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THE EFFICIENCY AND MECHANISMS FOR POLLUTANT REMOVAL IN
BIOLOGICAL WASTEWATER TREATMENT SYSTEMS

Kimberley A. Cameron
Department of Agricultural and Biosystems Engineering
McGill University, Montreal
August 2001
A thesis submitted to the Faculty of Graduate Studies and Research
in partial fulfilment of the requirements of the degree of
Master of Science
Kimberley A. Cameron, 2001
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Suggested short title:
POLLUTANT REMOVAL IN BIOLOGICAL
WASTEWATER TREATMENT SYSTEMS
M.Sc.
ABSTRACT
Agricultural and
Biosystems Engineering
The Efficiency and Mechanisms for Poilutant Removal
in Biological Wastewater Treatment Systems
The research project was initiated to refine the knowledge available on the treatment of
rural municipal wastewater by constructed wetlands. Field and laboratory studies were
conducted to determine the treatment capacity of a constructed wetland system and to
determine a substrate that would be most efficient as a phosphorus adsorption filter. The
wetland system consisted of three free-water surface cells, three blast fumace slag filters
and a vegetated filter strip, treating municipal wastewater. Bimonthly water samples at the
inlet and outlet of each component of the wetland system were analysed for biochemical
oxygen demand, nitrate and nitrite, ammonia and ammonium, total Kjeldahl nitrogen,
total suspended solids, total phosphorus, ortho-phosphate, fecal coliforms and E. coli.
Phosphorus and nitrogen concentrations were determined in the sediment, plant tissue and
water column of the free-surface wetland cells. The free-surface wetland cells achieved
removals as follows: ammonia and ammonium (52%), total Kjeldahl nitrogen (37%), total
suspended solids (93%), total phosphorus (90%) and ortho-phosphate (82%). The
vegetated filter strip achieved removals as follows: ammonia and ammonium (28%), total
Kjeldahl nitrogen (11 %), total suspended solids (22%), total phosphorus (5%) and ortho-
phosphate (0%). The slag filters reduced total phosphorus by more than 99%. Phosphorus
adsorption measurements were conducted on slag, calcite and shale. Slag was found to be
the most effective at removing phosphate.
M.Sc.
RESUME
Gnie agricole et
des biosystmes
L'efficacit et mcanismes de dpollution sous divers systmes de biopuration
Des tudes sur le terrain et en laboratoire furent entreprises afin de dterminer la capacit
d'puration de marais artificiels et quel substrat serait le plus fficace comme filtre
adsorptif pour le phosphore. Le systme de marais artificiels surface libre, servant
l'puration d'eau uses municipales tait constitu de trois cellules, un cran vgtal et
trois filtres de laitier granul de haut fourneau. Un chantillonnage bimestriel des eaux
l'exutoire des marais fut entrepris. Ces chantillons furent analyss pour leur demande
biochimique d'oxygne, les teneurs en nitrates et nitrites, ammoniac et ammonium, azote
total Kjeldahl, matires en suspension, phosphore total, orthophosphate, colibacilles
fcaux et E. coli. Les concentrations en phosphore et azote des sdiments du fond, des
tissus vgtaux et de la colonne d'eau des marais surface libre furent aussi dtermines.
L'adsorption du phosphore sur du laitier, de la calcite, et de la shale fut mesur.
Le systme de marais artificiels surface libre a atteint les niveaux de dpollution
suivants: ammoniac et ammonium (52%), azote total Kjeldahl (37%), matires en
suspension totales (93%), phosphore total (90%) et orthophosphates (82%). L'cran
vgtal a atteint des niveaux de dpollution suivants: ammoniac et ammonium (28%),
azote total Kjeldahl (11 % matires en suspension totales (22%), phosphore total (5%) et
orthophosphates (0%). Les filtres de laitier rduisirent le phosphore total par plus de 99%.
Lors des essais en laboratoire d'adsorption du phosphate, le laitier fut la matire la plus
efficace dans l'enlvement du phosphate.
li
ACKNOWLEDGEMENTS
l would like to thank the following people for their help during the course of the study:
Dr. Chandra Madramootoo, my thesis supervisor, for his guidance and motivation.
McGill University, Alfred College of Guelph University and the Corrugated Plastic Pipe
Association for financial support of the project.
The Research in Transfer Technology Sector of Alfred College of the University of
Guelph. l wish to thank Anna Crolla in particular for her invaluable guidance, patience
and support during the year of field and lab experiments. Martin Perron for his enthusiasm
and labour-intensive aid. Eric Brunet for the construction of the columns. Chris Kinsley
for his advice. Mary, Eric and Jamie for their help in the lab and field.
My co-researchers at Brace: Anita La Mendola, Bano Mehdi, Rebecca Short, Rikke Dam,
Ian Callum, Patrick Handyside, Chris Cox and Andrew Jamieson for their moral support
and valuable information.
Dr. P. Dutilleul for the statistics consultations. Dr. DJ. Lewis for his suggestions for
wetland soil sampling devices. Dr. C. Begg for her counsel on soil chemistry. George
Dodds for the translation of the abstracto Hlne Lalande for her contribution to the lab
analyses. Accutest Laboratories ofNepean, Ontario for the lab analyses.
Wendy Ouellette and Diane Chan-Hum for their excellent administrative skills.
Finally, to aIl of my family and friends who have been supportive during the months of
research. A special thanks to my parents for their endless encouragement and support
throughout aIl of my academic years of study and to Kevin for always being there.
111
TABLE OF CONTENTS
Abstract i
Rsum ii
Acknowledgements .iii
List of Tables vii
List of Figures , .ix
List of Appendices x
Nomenclature xiii
1. INTRODUCTION 1
1.1 Objectives 1
1.2 Scope '" 2
2. LITERATURE REVIEW 3
2.1 The Need for Wastewater Management 3
2.2 Pol1utants Present in Municipal Wastewater 4
2.2.1 Biochemical oxygen demand 4
2.2.2 Suspended solids 4
2.2.3 Pathogens 5
2.2.4 Nitrogen , 6
2.2.5 Phosphorus 7
2.3 Conventional Treatment Systems 8
2.4 Constructed Wetlands For Water Quality Improvement 8
2.4.1 Biological oxygen demand Il
2.4.2 Suspended solids 11
2.4.3 Pathogens , " .11
2.4.4 Nitrogen 12
2.4.4.1 The nitrogen cycle .12
2.4.4.2 Nitrogen removal by wetlands 13
2.4.5 Phosphorus , 15
IV
2.5 Phosphorus Polishing Steps 16
2.5.1 Vegetated filter strips 16
2.5.2 Phosphorus adsorption filters 17
2.5.2.1 Blast fumace slag 19
2.5.2.2 Calcite 19
2.5.2.3 Shale 20
2.6 Summary of Literature Review 21
3. MATERIALS AND METHODS 22
3.1 Site Description 22
3.2 Constructed Wetland System 26
3.2.1 Initial wetland conditions , 26
3.2.1.1 Sediment sampling and analysis 26
3.2.1.2 Plant sampling and analysis 28
3.2.1.3 Water sampling and analysis 28
3.2.2 Bimonthly water sampling and analysis 29
3.2.3 Monthly groundwater sampling and analysis 30
3.3 Phosphorus Polishing Step 30
3.3.1 Media for phosphorus removal 30
3.3.2 Description of soil materials 30
3.3.3 Phosphate adsorption measurement 31
3.3.4 Column experiments 32
4. RESULTS AND DISCUSSION 36
4.1 Initial Wetland Conditions 36
4.1.1 Sediment samples 36
4.1.2 Plant samples 38
4.1.3 Water samples 38
4.2 Bimonthly Water Sampling .42
4.2.1 Constructed wetland cells .42
v
4.2.2 Vegetated filter strip .45
4.2.3 Slag filters 46
4.3 Monthly Groundwater Sampling .46
4.4 Substrate for Phosphorus Adsorption Filters .48
4.4.1 Description of soil materials .48
4.4.2 Phosphate adsorption measurement .48
4.4.3 Column experiments 51
4.4.3.1 Slag - lower influent concentrations 51
4.4.3.2 Slag - higher influent concentrations 56
4.4.3.3 Calcite 57
4.4.3.4 Shale 60
5. CONCLUSIONS 63
5.1 Summary 63
5.2 General Conclusions 63
6. DIRECTIONS FOR FURTHER RESEARCH 65
REFERENCES 66
APPENDICES 73
A. Figures ofnitrogen and phosphorus concentrations of the sediment,
plant and water samples taken from the wetland cells 73
B. Influent and effluent concentrations from different stages in the
Alfred Municipal Wetland 79
C. Column experiments - slag - lower influent concentrations 84
D. Column experiments - slag - higher influent concentrations 89
E. Column experiments - calcite 94
F. Column experiments - shale 99
vi
Table 4.1
Table 4.2
Table 4.3
Table 4.4
Table 4.5
Table 4.6
Table 4.7
Table 4.8
Table 4.9
Table 4.10
Table 4.11
Table 4.12
Table 4.13
Table 4.14
Table 4.15
LIST OF TABLES
Page
Average influent pollutant concentrations to FSW l,
May 19 to November 3,2000 42
Summary of mean performance of the Alfred Municipal Wetland from
May 19 to November 3,2000 44
Average concentrations at the inlet and outlet of the wetland cells
from May 19 to November 3, 2000 45
Results ofmonthly groundwater samples from June to November 2000.47
Material characteristics 48
Results of shaker experiments run for 48 hours at initial phosphate
concentrations of 0.5, 1.0,3.0 and 5.0 g P0
4
L-
1
.49
Coefficients of Freundlich and Langmuir adsorption isotherms for slag,
shale and calcite , 49
Freundlich isotherm constants ofvarious substrates 50
Phosphate concentrations in effluent samples from columns
SL2-1, SL2-2 and SL2-3 taken February 2,2001 54
Filtered and unfiltered samples from columns SL2-1 and SL2-2
analysed for phosphate concentration (mg L-
1
) by Accutest Labs
and the CUITent study 54
Ca/P ratios of calcium phosphate compounds 55
Phosphate concentrations in effluent samples from columns SL15-1,
SL15-2 and SL15-3 taken February 2,2001 56
Percent phosphate removal and pH measurements for columns
CA15-1, CA15-2 and CA15-3 57
Comparison of the physical properties and experimental conditions
of the current study with other studies 58
Percent phosphate removal and pH measurements for columns
SH15-1, SH15-2 and SH15-3 60
VII
Table 4.16 Comparison of the physical properties and experimental conditions
of the CUITent study with that of Drizo et al. (1999) 60
viii
Figure 3.1
Figure 3.2
Figure 3.3
Figure 3.4
Figure 3.5
Figure 4.1
Figure 4.2
Figure 4.3
Figure 4.4
Figure 4.5
LIST OF FIGURES
Page
Aerial photograph of the Alfred Municipal Wetland and the
municipal sewage lagoons 24
Schematic of the constructed wetland system 25
Schematic of sample locations of the initial wetland conditions
sampling 27
Schematic of the column set-up 33
Experimental set-up for column experiments 35
Mean sediment concentrations in FSW 1and FSW II of the
Mean plant tissue concentrations in FSW 1and FSW II of the
Mean water concentrations in FSW l, FSW II and AB of the
Alfred Municipal Wetland .40
Shaker experiment results for slag, calcite and shale with an initial
phosphate concentration of 15 mg L-
1
for 4,8,24 and
48 hours 52
Shaker experiment results for calcite and shale with an initial
1
sampled at 4,8,24 and
48 hours 53
IX
LIST OF APPENDICES
Appendix A. Figures of nitrogen and phosphorus concentrations of the sediment,
plant and water samples taken from the wetland cells 73
A.1 Sediment nitrogen concentrations in each subplot of the Alfred Municipal
Wetland 74
A.2 Sediment phosphorus concentrations in each subplot of the Alfred Municipal
Wetland 75
A.3 Plant phosphorus and nitrogen concentrations in each subplot of the Alfred
Municipal Wetland 76
AA Water nitrogen concentrations in each subplot ofthe Alfred Municipal
Wetland 77
A.5 Water total phosphorus concentrations in each subplot of the Alfred Municipal
Wetland 78
Appendix B. Influent and effluent concentrations from different stages in the Alfred
Municipal Wetland 79
B.I Influent and effluent concentrations of BOD
s
and TKN from different stages in
the Alfred Municipal Wetland at each sampling date from May 19 to
November 3,2000 80
B.2 Influent and effluent concentrations ofNH
4
and TSS from different stages in
November 3, 2000 81
B.3 Influent and effluent concentrations ofTP and O-P0
4
from different stages in
November 3, 2000 82
BA Influent and effluent levels of FC and E. coli from different stages in
November 3, 2000 83
Appendix C. Column experiments - slag - lower influent concentrations 84
C.1 Mean percent phosphate removed and pH at port 1 for columns SL2-1,
SL2-2 and SL2-3 85
x
SL2-2 and SL2-3 86
SL2-2 and SL2-3 87
CA Mean percent phosphate removed and pH at port 4 for columns SL2-l,
SL2-2 and SL2-3 88
Appendix D. Column experiments - slag - higher influent concentrations 89
D.1 Mean percent phosphate removed and pH at port 1 for columns SL15-l,
SL15-2 and SL15-3 " 90
SL15-2 and SL15-3 91
SL15-2 and SL15-3 92
DA Mean percent phosphate removed and pH at port 4 for columns SL15-l,
SL15-2 and SL15-3 93
Appendix E. Column experiments - calcite 94
E.l Mean percent phosphate removed and pH for columns CA15-l,
CA15-2 and CA15-3 combined for port 1 95
E.2 Mean percent phosphate removed and pH for columns CA15-l,
E.3 Mean percent phosphate removed and pH for columns CA15-l,
CA15-2 and CA15-3 combined for port 3 '" 97
EA Mean percent phosphate removed and pH for columns CA15-l,
Appendix F. Column experiments - shale 99
F.l Mean percent phosphate removed and pH for columns SH15-l,
SH15-2 and SH15-3 combined for port 1 100
F.2 Mean percent phosphate removed and pH for columns SH15-l,
xi
F.3 Mean percent phosphate removed and pH for columns SHI5-1,
FA Mean percent phosphate removed and pH for columns SHI5-1,
xii
%:
AB:
Al:
Ah0 3:
BFS:
BOD:
BOD
s
:
Ca:
CaC0
3
:
CaO:
Ce:
CUS04:
CW:
CWRA:
d:
E. coli:
FC:
Fe:
FeO:
FSWI:
FSW II:
GWl:
GW2:
GW3:
GW4:
H
2
S0
4
:
ha:
h:
K:
KI:
K2:
K2HP04:
K
2
S0
4
:
KCI:
kg:
L:
M:
mg:
mL:
n.d.:
Nia:
n:
N:
NOMENCLATURE
Percent
Aerobic Basin
Aluminium
Aluminium Oxide
Blast Fumace Slag
Biological Oxygen Demand
Five-day Biological Oxygen Demand
Calcium
Calcium Carbonate
Calcium Oxide
Equilibrium Concentration of Adsorbate in Solution after Adsorption
Copper Sulfate
Constructed Wetland
Canadian Water Resources Association
Day
Escherichia coli
Fecal Coliform
Iron
Iron Oxide
Free-surface Wetland Cell l
Free-surface Wetland Cell II
Groundwater Sampling Location 1
Sulfuric Acid
Hectare
Hours
Freundlich Constant
Constant in Langmuir Equation
Constant in Langmuir Equation
Dipotassium Hydrogen Phosphate
Potassium Sulfate
Potassium Chloride
Kilogram
Litre
Molarity
Milligram
Millilitre
Not Determined
Information Not Available
Measure of the Nonlinearity in Freundlich Equation
Nitrogen
XIll
N:
N2:
N
2
0:
NH
3
:
NH
4
:
nm:
NO:
N02:
N03:
OME:
O-P0
4
:
Org-N:
P04:
PVC:
R
2
:
rpm:
Se:
SS:
TC:
TKN:
TN:
TP:
TSS:
VFS:
WWC:
w/v:
WWV:
x/m:
n:
~ m :
Normality
Nitrogen Gas
Nitrous Oxide
Ammonia
Ammonium
Nanometre
Nitric Oxide
Nitrite
Nitrate
Ontario Ministry of the Environment
Ortho-phosphate
Organic Nitrogen
Phosphate
Polyvinyl Chloride
Correlation Coefficient
Rotations per Minute
Selenium
Suspended Solids
Total Coliform
Total Kjeldahl Nitrogen
Total Nitrogen
Total Phosphorus
Total Suspended Solids
Vegetated Filter Strip
World Water Council
Weight to Volume Ratio
World Water Vision
Amount of Adsorbate Adsorbed per Unit Weight of Adsorbent
Number of Replicates
Micrometer
XIV
1. INTRODUCTION
As the world population grows and an increasing amount of pollution is created, the
qua1ity of our freshwater supp1y may be jeopardized. From a global perspective,
governments are raising the standards for the qua1ity of wastewater being discharged into
receiving waters. In Canada, where 9% of the world's renewab1e fresh water exists
(McGill University, 1999), there is concern for the sustainabi1ity of this va1uab1e resource
and greater focus is being put on research into improving the quality of wastewater being
re1eased to surface waters.
To preserve the qua1ity of their freshwater, the provInce of Ontario has deve10ped
increasing1y stringent criteria for wastewater re1eased to surface waters (Ontario Office of
the Premier, 2000). In order for small rural municipa1ities, with 10wer tax bases and
1imited resources, to adopt wastewater treatment technologies, purifying techniques must
be 10w cost, require minimal maintenance, and be easi1y applicable. Conventiona1
advanced wastewater treatment typically requires large capital investments and consumes
large amounts of energy. This has stimu1ated the deve10pment of alternative wastewater
treatment systems which will be more efficient and 1ess expensive than conventiona1
treatment systems. Constructed wetlands may be a solution, and are growing in popu1arity
as a natura1 and economica1 alternative for purifying wastewater (Wood, 1995).
A pilot constructed wet1and system has been built in Alfred, Ontario and is being
eva1uated as a cost effective means to treat municipal 1agoon wastewater for the
municipa1ity. If proven successfu1, this techno10gy cou1d be used in numerous small rural
communities. The Alfred Municipal Wetland inc1udes phosphorus adsorption filters and a
vegetated filter strip as po1ishing steps.
1.1 Objectives
The broad objective of this study was to examine the efficiency and mechanisms for
pollutant remova1 in bio10gica1 wastewater treatment systems.
1
Specifie objectives were to:
1. Determine the removal for each wetland cell for biochemical oxygen demand,
nitrate and nitrite, ammonium and ammonia, total Kjeldahl nitrogen, total
suspended solids, total phosphorus and ortho-phosphate, fecal coliforms and
Escherichia coli (E. coli) by water samples;
2. Determine the phosphorus and nitrogen contents of the sediments at the bottom of
the wetland ceIls;
3. Determine the amount of phosphorus and nitrogen removed through plant uptake
during the growing season;
4. Evaluate the environmental impact of the wetland on the surrounding
groundwater;
5. Determine the effectiveness of the vegetated filter strip for reducing nutrient
concentrations in wastewater;
6. Determine a substrate medium which is effective in removing phosphorus from
wastewater in a post-wetland treatment stage.
1.2 Scope
The study of the constructed wetland system was conducted over one season of operation,
from May to November 2000, under the climatic conditions of Eastern Ontario. Due to
the large variability of natural systems, the results and recommendations of the
constructed wetland system study pertain only to similar conditions. The focus of the
study is limited to rural municipal wastewater treatment systems. Therefore, treatment
technologies for large urban municipalities are not discussed.
2
2. LITERATURE REVIEW
Greater focus is being put on the research into improving the quality of wastewater being
released into surface waters. In Canada, municipal sewage treatment systems have been
installed to treat 75% of the wastewater produced (McGill University, 1999). Therefore,
there is still a large portion of untreated wastewater being discharged directly to receiving
waters. Where sufficient diluting water is available, these higher effluent pollutant
concentrations are most often not a problem. Normally, effluent dilution of at least l 0: l
(uncontaminated receiving water:effluent) is required to meet regulatory criteria (Horne,
1995). Unfortunately, clean diluting water is becoming a scarce commodity in many areas
(Horne, 1995), and ultimately we may reach a point where the pollution entering the
receiving waters is greater than its natural assimilative capacity. It is imperative,
therefore, to develop a wastewater treatment system which will be economical, require
little maintenance, and be easily applicable.
2.1 The Need for Wastewater Management
Pathogens and nutrients are among the main pollutants present in municipal wastewater
from small rural areas which require treatment before being discharged to surface waters.
Pathogens are disease-producing organisms that grow and muitiply within the host. Their
control is one of the fundamental reasons for wastewater management and many
regulatory agencies specify bacteriallimits on discharges to surface waters. Regardless of
the existing regulations, there have been instances when pathogens escaped the
monitoring system and contaminated the water supply. For example, in May of 2000, the
town on Walkerton, Ontario was faced with the crisis of deadly E. coli contamination in
their drinking water. Six people died, 2,300 others became ill (Verma and Donovan,
2000).
Nutrients are necessary in freshwaters as they support aquatic life. However, too large a
nutrient loading may lead to eutrophication of the water body. A eutrophie water body is
rich in nutrients and therefore supports a dense plant population, which kills animal life
3
by depriving it of oxygen. Wastewater is a major source of nutrients that can cause
eutrophication of lakes and streams and deterioration of water quality, even after
secondary treatment (Nichols, 1983).
2.2 Pollutants Present in Rural Municipal Wastewater
Rural municipal wastewater consists most often of a combination of domestic and
commercial wastewaters. The pollutant parameters commonly present are biological
oxygen demand, suspended solids, pathogens, ammonium, nitrate-nitrites, organic-
nitrogen, total Kjeldahl nitrogen, inorganic phosphorus and organic phosphorus (Kadlec
and Knight, 1996). Trace metals and organic pollutant molecules may also be present.
2.2.1 Biochemical oxygen demand
According to Standard Methods for the Examination ofWater and Wastewater (American
Public Health Association, 1989), the biochemical oxygen demand (BD) determination
is an empirical test in which standardized laboratory procedures are used to determine the
relative biological oxygen requirements of wastewater, effluents, and polluted waters.
The test measures the oxygen required for the biochemical degradation of organic
material and to oxidize inorganic material during a specified incubation period.
2.2.2 Suspended solids
Suspended solids are matter suspended in the water profile. Turbidity in water is caused
primarily by suspended matter. Increased turbidity reduces the quality of water by
impeding sunlight from penetrating the water column. As a result, there may be decreased
photosynthesis, which may lead to reduced dissolved oxygen content in the water. The
suspended solids (SS) concentration of extremely clean waters is below 1 mg L-
1
and
ranges to over 100 mg L-
1
for highly turbid waters. Levels for sewage and for storm-water
overflows can be even higher.
4
2.2.3 Pathogens
Pathogens are disease-producing organisms that grow and multiply within the host. They
are divided into categories with the most common groups associated with water pollution
being bacteria, viruses, protozoa, helminths (intestinal worms) and algae.
Measurement of pathogenic organisms is expensive and technically challenging, therefore
indicator organisms have been identified that are easy to monitor and correlate with
populations of pathogenic organisms. The coliform bacteria group is one of the most
common indicator organisms. Coliforms are frequently monitored as total or fecal
coliforms. Total coliform (TC) is defined as a large group of anaerobic, non-spore
forming, rod-shaped bacteria that ferment lactose with gas formation within 48 hours at
35C (Chapra, 1997). They originate most often in the intestinal tract of warm-blooded
animaIs, inc1uding humans, but may also exist in soils. E. coli is a common member of
this group. Sorne pathogens enter the human body through the skin but more commonly
they are ingested with drinking water. Fecal coliform (FC) is a subset of TC that cornes
from the intestines of warm-blooded animaIs. However, since they do not inc1ude soil
organisms, they are preferable to TC as an indicator organism. They are measured by
running the standard total coliform test at an elevated temperature (44.5C).
Loading concentrations of coliforms depend on the extent of water use in a region. For
example, in the United States, where per capita water use is high, the coliform
concentration of raw sewage is approximately 20 x 10
6
TC per 100 mL. In a country like
Brazil, however, where water consumption lS lower, concentrations of
200 x 10
6
TC per 100 mL have been measured (Chapra, 1997). The concentration
standards for water uses in the United States may give a general idea of acceptable
coliform counts. Drinking water has a zero-tolerance limit for both TC and FC. Contact
recreation has a TC 1imit of 1000-5000 per 100 mL and a FC 1imit of 100-
1000 per 100 mL (Chapra, 1997).
5
2.2.4 Nitrogen
The forms of nitrogen of greatest interest in waters and wastewaters are nitrate (NO]-),
nitrite (N02-), ammonium (NH/), and organic nitrogen (Org-N). All these forms of
nitrogen, as well as nitrogen gas (N2), are components of the nitrogen cycle and are
biochemically interconvertible (American Public Health Association, 1989). Total
nitrogen (TN) is simply the sum of the various nitrogen forms. The total nitrogen
concentration in municipal wastewaters ranges from 15 to over 50 mg L-
l
, on average
(Reed et al., 1995).
Nitrate generally is found in minute quantities in surface water but may attain high levels
in sorne groundwater. In excessive amounts, it contributes to the illness known as
methemoglobinemia in infants. The Canadian Water Quality Guidelines, developed by
Environment Canada, has imposed a limit of 10 mg nitrate-nitrogen L-
l
on drinking water
to prevent this disorder (Agriculture and Agrifood Canada, 2000b). Nitrate is found only
in small amounts in fresh domestic wastewater but in the effluent of nitrifying biological
treatment plants nitrate may be found ln concentrations of up to
30 mg nitrate-nitrogen L-
l
. It is an essential nutrient for many photosynthetic autotrophs
and in sorne cases has been identified as the growth-limiting nutrient (American Public
Health Association, 1989). In excess amount, nitrate leads to eutrophication. One mg L-
I
of nitrate-nitrogen is sufficient to cause eutrophication in freshwaters (Horne, 1995).
Streams where flows are dominated by domestic wastewater or agricultural return water
have nitrate levels between 2 and 15 mg L-
l
, and on occasion sorne may exceed 50 mg L-
I
(Horne, 1995).
Nitrite is an intermediate oxidation state of nitrogen, both in the oxidation of ammonia to
nitrate and in the reduction of nitrate to nitrogen gas (American Public Health
Association, 1989).
Ammonia IS present naturally in surface and wastewaters. Ammonia may exist as
molecular ammonia (NH]) or as ammonium ions (NH4+). Ammonium concentration
generally is low in groundwaters because it adsorbs to clays and is not leached readily
6
from soils. In sorne cases it may be necessary to oxidize or otherwise remove the
ammonia form of nitrogen because it is toxic to many fish and other wildlife and can also
require a significant oxygen demand from the receiving water (Reed et al., 1995; Horne,
1995).
Organic nitrogen is defined as organically bound nitrogen in the trinegative oxidation
state. It consists of amino acids, urea and uric acid, and purines and pyrimidines.
Analytically, organic nitrogen and ammonia can be determined together and have been
referred to as Kjeldahl nitrogen, a term that reflects the technique used in their
determination. Typical organic nitrogen concentrations vary from a few hundred
micrograms per liter in sorne lakes to more than 20 mg L-
I
in raw sewage (American
Public Health Association, 1989).
The Canadian Water Quality Guidelines state that in order to protect aquatic life
freshwaters require a maximum nitrite concentration of 0.06 mg L-
I
, however, there are
no limits for N0
3
-N or TN (Agriculture and Agrifood Canada, 2000b).
2.2.5 Phosphorus
Phosphorus is not attributed to any known health disorder, however of all wastewater
constituents it is the most often associated with eutrophication of surface waters (Reed et
al., 1995). The total concentration of phosphorus in an ordinary domestic wastewater is
within the range of 6-20 mg P L-
I
(American Public Health Association, 1989). The
Canadian Water Quality Guidelines have not set a limit on the amount of phosphorus to
be released into open water bodies (Agriculture and Agrifood Canada, 2000b).
Phosphorus occurs in natural waters and in wastewaters almost solely as phosphates.
These are classified as orthophosphates, condensed phosphates (pyro-, meta-, and other
polyphosphates), and organically bound phosphates. Organic phosphorus may also exist.
Phosphorus as orthophosphate is one of the main nutrients responsible for eutrophication
(Lee et al., 1996).
7
The phosphate (P04) levels in many streams where flows are dominated by domestic
wastewater or agricultural return water range between 2-5 mg L-
1
P04-P, which creates
potential conditions for eutrophication (Home, 1995). Home (1995) recommends that
concentrations of P04-P be less than 0.1 mg L-
1
in effluents so as not to create
eutrophication.
Chemical precipitation with alum or sorne other flocculent, biological removal and land
treatment are among the methods used to remove phosphate from wastewaters (Home,
1995; Lee et al., 1996). The disadvantage of a conventional chemical precipitation
process lS that it produces excess chemical sludge and consumes large amounts of
chemicals. As well, chemical precipitation often requires high pHs for the process to
occur, therefore pH corrections of effluents must be done before discharged into receiving
waters. Finally, separation of the calcium phosphate precipitate may at times be a difficult
procedure (Roques et al., 1991). Land treatment is an attractive alternative since it does
not have any of these disadvantages.
2.3 Conventional Treatment Systems
Conventional wastewater treatment may be accomplished by physical, biological and
chemical processes. Physical treatment processes are usually the first stage of wastewater
treatment. Large solids and grit are removed at this stage. This may be achieved through
screening, aerated grit chambers or via sedimentation. Biological treatment is a secondary
treatment step. The principal secondary treatment technologies are facultative ponds,
aerated lagoons, activated sludge, trickling filters, and rotating biological contactors.
Chemical processes use chemical precipitation to remove a nutrient in a solid form. For
example, phosphorus may be precipitated and accumulate as sludge.
2.4 Constructed Wetlands For Water Quality Improvement
The concern over contamination of water systems with pathogens and the eutrophication
of surface waters has highlighted the need for upgrading the quality of wastewater before
its discharge. A potential solution may be the use of constructed wetlands; an economical,
natural alternative for the purification of wastewater. Additional benefits of the use of
8
constructed wetlands to treat wastewater are that they are aesthetically pleasing and serve
as a habitat for wildlife.
Wetlands are defined as land where the water table is at or above the ground surface long
enough to maintain saturated soil conditions and the growth of related vegetation.
Wetlands may be engineered and constructed expressly for water quality treatment.
There has been considerable research on the use of wetlands for treating wastewater
(Hammer, 1989; Mitsch and Jorgensen, 1989; Etnier and Guterstam, 1997; Sedlak, 1991;
Moshiri, 1993; Reed et al., 1995; Kadlec and Knight, 1996). Conventional advanced
treatment of wastewater typically requires large capital investments to build and operate
and requires large amounts of energy (Nichols, 1983). Constructed wetlands cost less to
build and operate and consume less energy than standard mechanical treatment
technology (Reed et al., 1995). As a result interest is increasing in the use of wetlands as a
cost and energy-effective alternative for removing nutrients from wastewater (Nichols,
1983). Wetlands can be designed and constructed to effectively increase the capacity of a
wastewater treatment system by further improving the quality of the effluent entering the
receiving water or they may provide complete treatment for small communities (Hiley,
1995). The most important economic disadvantage is the cost of land. However, as long
as sufficient land area is available for the required wetland size, a treatment wetland can
be a very attractive upgrade alternative (Pries and Phillips, 2000).
In Canada, treatment wetlands have been used for more than 35 years for polishing
wastewater and stormwater (Pries and Phillips, 2000). Constructed wetlands have also
been used successfully on a global basis as secondary and tertiary treatment of effluent in
the United States (Martin and Moshiri, 1994; Gale et al., 1994), the Netherlands
(Schreijer et al., 1997), Norway (Maehlum et al., 1995), and Australia (Mitchell et al.,
1995). There are several properties of constructed wetlands that make them adapted to the
treatment of wastewaters, including high plant productivity, large adsorptive surfaces on
sediments, plants, and roots, aerobic-anaerobic interfaces, and diverse, active microbial
populations (Maehlum et al., 1995).
9
Cold winter climate, as such is the case in many regions in Canada, can significantly
affect hydraulics, chemical and biochemical processes in constructed wetlands. System
performance on a seasonal basis may be affected by reduced physical and biological
activity as a result of dormant vegetation and the slow reaction rate for soil or aquatic
microbes at low temperatures (Maehlum et al., 1995). Many of the colder-climate
constructed wetland systems in Canada are therefore designed for seasonal discharge
(Pries, 1994).
Free-surface wetlands are the most popular type of wetland used for wastewater treatment
in North America (Brix, 1994). Free-surface wetlands are densely vegetated by a variety
of plant species that are adapted to continuous flooding and are suitable for receiving
continuous flows of wastewaters. They typically have water depths less than 0.4 m. The
design may include open water areas to provide for optimization of hydraulics and for
wildlife habitat enhancement. The wind provides the mixing energy required for the
physical mixing of nitrate-rich water into anoxic zones for the denitrification process. The
carbon, to be used by the bacteria as an energy source, is supplied by plants. Dead plant
fragments provide a surface for bacterial growth.
Knight et al. (1993) performed an inventory of municipal wastewater treatment systems
using constructed wetlands. There existed at the time 369 free-surface wetland cells in
North America, treating 98 systems at 85 sites treating flows in excess of 190 m
3
day"\.
Many of the systems have been constructed to provide advance treatment for an existing
treatment facility (Reed and Brown, 1992). One reason that free-surface wetlands are
popular is that they are aesthetically pleasing, due to their emergent macrophytes. In
addition, treatment life expectancies are very large. The life expectancy of a constructed
wetland is a minimum of 20 years and has been estimated to be more than 50 years (Pries
and Phillips, 2000). In fact, according to Kadlec (1995) although the technology of
constructed wetlands is relatively new, in existence since the 1970s (Kadlec and Knight,
1996), a free-surface wetland has never expired before its life limit.
10
Wetlands have a higher rate of biological activity than most ecosystems, therefore they
can transform many of the common pollutants that occur in conventional wastewaters into
harmless byproducts or essential nutrients that can be used for additional biological
productivity. Constructed wetland systems are effective at reducing biochemical oxygen
demand, suspended solids, fecal coliforms, ammonium, nitrates, and phosphorus in
wastewaters (Moshiri, 1993; Kadlec and Knight, 1996; Vymazal et al., 1998; Kadlec,
1995). It is important to note that there exists a minimum quantity of nutrients in wetlands
naturally. These nutrient levels are referred to as background levels. A wetland therefore
cannot be expected to reduce nutrients to below these naturally occurring values.
2.4.1 Biological oxygen demand
BaD removal by free-surface wetlands includes several chemical and biochemical
processes: aerobic respiration; fermentation; anaerobic reduction of nitrate, sulfate and
iron; and methanogenesis (Kadlec and Knight, 1996). Typical background levels of BaD
in free-surface wetlands are 5-15 mg L-
1
(Kadlec, 1995). Free-surface wetlands generally
reduce BaD down to these background levels (Reed et al., 1995).
2.4.2 Suspended solids
Most of the solids in the wastewater are removed by free-surface wetlands through
sedimentation and filtration, as vegetation obstructs flow and reduces flow velocities. In
many applications, a sedimentation pond is added upstream of the wetland cells to
promote the removal of larger suspended particles and minimizes the chance of clogging
the wetland ceUs. As a rule of thumb, a treatment wetland removes about three quarters of
the incoming total suspended solids (TSS), provided the incoming TSS is greater than
20 mg L-
1
(Kadlec and Knight, 1996). Free-surface wetlands serving as secondary
treatment may reduce TSS in effluents to values of 5-15 mg L-
1
(Reed et al., 1995).
2.4.3 Pathogens
Bacteria, viruses, and parasites are aU reduced by free-surface wetlands. Wastewater is a
hostile environment for pathogenic organisms. Natural dieback, temperature, ultraviolet
light, unfavourable water chemistry, predation, sedimentation and adsorption are the
11
factors contributing to the removal of pathogens from wetland systems (Reed et al., 1995;
Kadlec and Knight, 1996), with sorption and predation most likely the important
mechanisms involved in the reduction of these pathogens (Reed et al., 1995).
When inflow coliform populations are high, typical of untreated or partially treated
municipal wastewater that has not received disinfection, wetland removal efficiencies are
nearly always greater than 90% (Kadlec and Knight, 1996). Warm blooded animaIs that
inhabit the wetland contribute to background levels of fecal coliforms ranging from 50-
1000 FC per 100 mL (Kadlec, 1995).
2.4.4 Nitrogen
2.4.4.1 The nitrogen cycle
There are five principal processes that transform nitrogen from one form to another
within a wetland: ammonification, nitrification, denitrification, nitrogen fixation, and
nitrogen assimilation.
Ammonification is the biological transformation of organic nitrogen to ammonia. Up to
100% of the organic nitrogen in many wastewaters is readily converted to ammonia
(Kadlec and Knight, 1996).
Wittegren and Tobiason (1995) describe the process of nitrification-denitrification as
follows: NH
4
+ ions present in wastewater may be sorbed to cation exchange sites at the
surfaces of organogenic sediments and plant litter. When exposed to oxygen-rich water or
air the NH/ would likely be converted to N0
3
- (nitrification). Nitrification is the
principal transformation mechanism that reduces the concentration of ammonia in many
wetland treatment systems. When anaerobic conditions become present, the N0
3
- could be
denitrified with organic matter acting as the carbon and energy source, producing
nitrogen gas (N2), nitrous oxide (N20), or nitric oxide (NO). The formulas for nitrification
(equation 2.1) and denitrification (equation 2.2) are expressed below according to Chiang
et al. (1999):
12
[2.1]
[2.2]
Nitrogen fixation is the process by which nitrogen gas in the atmosphere diffuses into
solution and is reduced to ammonia nitrogen by bacteria, algae and higher plants.
Nitrogen assimilation is the process whereby inorganic nitrogen forms are converted into
organic compounds.
2.4.4.2 Nitrogen removal by wetlands
The total nitrogen removal in free-surface wetlands is often greater than SO% (Brix,
1994). The background levels of nitrogen forms in free-surface wetlands as reported by
Kadlec and Knight (1996) are as follows: nitrate-nitrogen is approximately zero,
ammonium nitrogen is approximately zero in summer, but is non-zero in winter, and
organic nitrogen is approximately 1.S mg L-
1
. Nitrite is not chemically stable in most
wetlands and is generally found in very low concentrations.
The potential mechanisms for nitrogen removal in wetland systems are plant uptake,
volatilization of ammonia, and denitrification (Crites et al., 1997; Gersberg et al., 1983;
Hiley, 1995).
Nitrogen is removed by growth of large wetland plants but, since most freshwater
macrophytes have their roots in the soil, they remove little nitrogen from surface water.
The main drawback with an uptake-for-growth system is the need to remove and dispose
of the very large amount of biomass which will fill up the marsh or, worse, recycle
organic nitrogen and ammonium back into the system when decomposition occurs in
winter (Kadlec, 1995).
13
Ammonia volatilization is the process by which ammonia is removed from solution to the
atmosphere through diffusion through water upward to the surface and through mass
transfer from the water surface to the atmosphere.
The major pathway for nitrogen removal in constructed wetlands is nitrification followed
by denitrification (Brix, 1994). Denitrification can be induced anywhere if the appropriate
conditions are supplied. These conditions are: oxygen levels less than 0.2 mg L-
1
; a
physical site where the bacteria required in the process attach; a supply of carbon food; a
supply of nitrate (Home, 1995). Armstrong and Armstrong (1988) suggest that the matrix
of aerobic and anaerobic environments which can develop in a wetland can achieve de-
nitrification at the same time as nitrification.
Denitrification is the ideal solution to nitrate pollution because it removes the problem
permanently since the waste product is N2 gas, which is released into the N2 reservoir in
the atmosphere. Since N2 is present in such large amounts in the atmosphere,
denitrification in a constructed wetland will not alter its concentration to any extent
(Home, 1995). In addition, because the waste product is agas, there is no build-up of
sludge or biomass, and therefore no sludge removal or disposaI is needed.
Rates of nitrate removal of 200 to over 5,000 mg m-
2
d-
1
can be achieved with initial
nitrate values of 2-14 mg L-
1
(Home, 1995). Home (1995) found that in two weeks
20 mg L-
1
N03-N can be reduced to less than 1 mg L-
1
, primarily as a result of bacterial
denitrification.
The oxygen required for nitrification is delivered either directly from the atmosphere
through the water or sediment surface, or by leakage from plant roots. Oxygenation is
often the limiting step for nitrogen removal, and therefore the design of the wetland and
the type and composition of the wastewater will influence its removal (Brix, 1994).
Wittgren and Tobiason (1995) concluded in their study of a free-surface wetland that
oxygen deficiency was unlikely to limit nitrification. Instead, they believe that sub-
optimal hydraulic loading conditions, a lack of suitable surfaces for ion exchange ofNH4+
14
and for the attachment of nitrifiers, and phosphorus deficiency were considered
potentially important factors in limiting nitrification.
2.4.5 Phosphorus
Research on the ability of wetland systems to remove phosphorus has been conducted
worldwide, such as in the United States (Moshiri, 1993; Kadlec and Knight, 1996),
Australia (Mann and Bavor, 1993), Denmark (Schierup et al., 1990), Norway (Zhu et al.,
1997), the United Kingdom (Drizo et al., 1997), the Czech Republic (Vymazal, 1995),
Sweden (Johansson, 1997), and the Netherlands (Schreijer et al., 1997). However,
constructed wetlands have been found to be limited in their ability to effectively remove
phosphorus from wastewater in the long-term (Mann and Bavor, 1993; Mann, 1997;
Kadlec and Knight, 1996). Their phosphorus removal capacity is estimated to be only
2-5 years (Drizo et al., 1999). Richardson (1985) concluded that wetlands may be both a
source and sink for phosphorus. Initially the removal rates will be high; however, after
several years phosphorus will be released from the wetland, once the phosphorus in the
treated water has a lower concentration than that found in the wetland.
Immobilization of phosphorus in constructed wetland systems occurs through microbial
and plant uptake, incorporation into orgamc matter, and substratum adsorption and
chemical precipitation (Kadlec and Knight, 1996; Richardson, 1985; Davies and
Cottingham, 1993, Brix et al., 2000; Mann 1997). The microbial pool is small and quickly
becomes saturated (Richardson, 1985). According to Richardson (1985), rooted emergent
wetland vegetation removes substantial quantities of phosphorus, but after tissue death
35-75% of the plant phosphorus is released back to the system. Thus, it has been
suggested that vegetation serves only as a short-term sink for phosphorus unless the
biomass is harvested (Lantzke et al., 1998, Richardson, 1985). However, Brix (1994,
1997) found that only an insignificant fraction of the amount of phosphorus loaded into
the system can actually be removed by harvesting the plant biomass. Annual peat
accumulations of phosphorus are very limited and range from 0.05-2.4 kg ha-
1
(Richardson, 1985).
15
It is suggested that the substrate may play the greatest role in phosphorus removal in a
constructed wetland (Mann, 1990; Drizo et al., 1999). According to Zhu et al. (1997) the
phosphorus-removal capacity of a substrate is dependent upon both the physical and
chemical properties of the media. Physical properties important to consider may include
particle size, porosity, available surface area, and hydraulic conductivity (Mann and
Bavor, 1993; Zhu et al., 1997). For example, a porous medium with a small particle size
would allow for a large surface area, enhancing the potential for phosphorus sorption
capacity. However hydraulic conductivity may be compromised with fine grained
particles, in which case plugging may occur.
Redox conditions, pH, ionic strength, anaerobic and aerobic conditions, as weIl as iron
(Fe), aluminium (Al), and calcium (Ca) contents are among the chemical characteristics
that affect substratum phosphorus-sorption (Davies and Cottingham, 1993; Nichols, 1983;
Stumm and Morgan, 1981; Brix et al., 2000, Mann and Bavor, 1993; Moore and Reddy,
1994; Vymazal et al., 1998; Zhu et al., 1997). Phosphorus may be bound in the substrate
medium as a consequence of adsorption and precipitation reactions with Fe, Al, and Ca.
When the pH of the wastewater is greater than 6, both physical adsorption to Fe and Al
oxides and precipitation as calcium phosphates, in the forms of hydroxyapatite (Mann and
Bavor, 1993) and fluoroapatite, contribute to the removal of phosphorus from solution.
When the pH is decreased be10w 6, iron and aluminium phosphates precipitate in the
forms of strengite (Fe(P04)2H20) and variscite (AI(P04)2H20) (Gerritse, 1993).
A post wetland phosphorus po1ishing step may therefore be required to achieve
sustainable reduced levels of phosphorus in the system. A phosphorus po1ishing step may
be in the form of a vegetated filter strip or a phosphorus adsorption filter.
2.5 Phosphorus Polishing Steps
2.5.1 Vegetated fiUer strips
A vegetated filter strip is a land treatment process in which wastewater is treated as it
flows over grass-covered slopes. They are often referred to as buffer strips or zones, grass
strips, riparian planting, or overland flow filters. As the water flows through the dense
16
vegetation on the slope, particulate pollutants settle out and dissolved constituents are
sorbed by plants and soils. The organic fraction of the settled particulates is microbially
oxidized, and sorbed nutrients, primarily inorganic nitrogen and phosphorus, are
incorporated in biomass, microbially transformed by nitrification, or bound in the soil
layer. A portion ofthe nutrients are removed when the vegetation is harvested.
Studies by Chaubey et al. (1994) identified removal rates in the order of 67% to 92% for
total phosphorus. The results of research conducted on a total of Il vegetated filter strips
in Finland, Norway, Sweden, and Denmark showed that total phosphorus was effectively
diminished, with removals of 27 to 97% (Uusi-Kamppa et al., 2000). The retention
increased with increasing filter strip width. The upper part of the filter strips played an
important role in phosphorus removal due to sedimentation as a retention process.
Bacteria may also be removed by filter strips. Bacteria removals on average range from
38 to 89% (Hiley, 1995). This process could provide a very safe and relatively
inexpernsive form of disinfection for sewage effluents from small to medium
communities.
2.5.2 Phosphorus adsorption filters
Phosphorus removal may be achieved in a permanent manner using a constructed filter
composed of an adsorptive medium. Numerous natural and artificial media have been
studied for their capacity to remove phosphorus from wastewater (Slag by Yamada et al.,
1986, Johansson, 1999, Baker et al., 1998, Lee et al., 1996, Mann, 1997, Mann and
Bavor, 1993 and Sakadevan and Bavor, 1998; Granular activated magnesia clinker by
Kaneko and Nakajima, 1988; Light weight aggregates by Zhu et al., 1997; Calcite by
Freeman and Rowell, 1981 and Brix et al., 2000; Sand by Aulenbach and Meisheng,
1988; Half-burned dolomite by Roques et al., 1991; Peat and sand amended with iron
oxides or steel wool by James et al., 1992; Amended sand with red mud by Ho et al.,
1992; LECA by Johansson, 1997; Shale by Drizo et al., 1997; Gravel and industrial waste
substrata by Mann and Bavor, 1993; Sediments by Fox et al., 1989; Activated alumina
adsorbent by Hano et al., 1997; Limestone and metal oxides by Blowes et al., 1999;
Minespoil by Peterson et al., 1998; Peat by Brooks et al., 1984 and Rock et al., 1984).
17
In selecting a substrate for a phosphorus filter, it is important to select a medium which
has a high phosphorus adsorption capacity (Brix et al., 2000; Johansson, 1997). To aid in
the comparison of various adsorption media, the results obtained from phosphorus
adsorption measurements are often fit to adsorption isotherms. The relationship between
the amount of material adsorbed and the equilibrium concentration at constant
temperature is called an adsorption isotherm. Two of the more common isotherms used
are called the Freundlich and Langmuir adsorption isotherms. The Freundlich equation,
an empirical equation, implies that the affinity for adsorption decreases exponentially
with increasing saturation, whereas the Langmuir equation assumes constant binding
energy (Kuo and McNeal, 1984). The Freundlich K value gives a measure of relative
phosphorus adsorption capacity, where a higher K value equates to greater phosphorus
adsorption capacity (Sakadevan and Bavor, 1998). The Freundlich isotherm is defined as
follows:
ln(x/m) = ln K + lin ln Ce [2.3]
where x/m is the amount of adsorbate adsorbed per unit weight of adsorbent, Ce is the
equilibrium concentration of adsorbate in solution after adsorption, K is referred to as the
Freundlich constant, and n is the measure of the nonlinearity involved (Stumm and
Morgan, 1986). The Langmuir adsorption isotherm is defined as follows:
[2.4]
where KI and K2 are constants, x/m is the amount of adsorbate adsorbed per unit weight
of adsorbent, and Ce is the equilibrium concentration of adsorbate in solution after
adsorption (Stumm and Morgan, 1986).
From prevlOus research conducted by authors mentioned earlier, blast fumace slag,
calcite and shale were found to be highly successful at removing phosphorus. The
suitability of these materials for use in an additional phosphorus adsorption filter was
warranted in view of their appropriate chemical characterization in terms of phosphorus
18
removal capacity and their success in previous studies. These media are inexpensive and
locally available, which reduces the costs of the constructed wetland system. This was the
case for the three media chosen for this study.
2.5.2.1 Blast furnace slag
Blast fumace slag, as defined by Mann and Bavor (1993) is a calcium-aluminium silicate
by-product of iron production. Although there exist variations in the composition of slag,
depending on the iron used in production, in general slags contain high aluminium and
iron concentrations which contribute to phosphorus adsorption. They also contain a high
proportion of calcium oxide which assists in the precipitation of calcium phosphates.
Blast fumace slag has been tested in batch and column experiments (Mann and Bavor,
1993; Baker et al., 1998; Sakadevan and Bavor, 1998; Johansson, 1999; Lee et al., 1996;
Mann, 1997). The results of these investigations show that slag has a strong phosphorus
removal potential. Johansson (1999) described the phosphorus adsorption capacity of slag
as being high to very high. The sorption experiment indicated that the removal of
phosphorus by the slag columns at the end of the experiment exceeded 95%. Sakadevan
and Bavor (1998) concluded that up to 44 g of phosphorus can be removed per kg of slag
media. Mann (1997) reported phosphorus adsorption capacities greater than 380 mg kg-
I
for various slags. Research conducted by Yamada et al. (1986) found that steelworks slag
had a phosphorus adsorption capacity of 34 mg kg-l, Mann (1997) attributed the high
phosphorus adsorption capacity of the slags to the formation of calcium-phosphorus
complexes at high pH, such as calcium hydroxyapatite and octacalcium phosphate and
dicalcium phosphate. Yamada et al. (1986) found that phosphate adsorption increased on
slags with larger porosities.
2.5.2.2 Calcite
Calcite is defined as being composed of one hundred percent calcium carbonate (CaCO)).
Several studies have been conducted on the ability of calcite or CaCO)-containing media
to remove phosphorus from solution (Freeman and Rowell, 1981; Aulenbach and
Meisheng, 1988; Brix et al., 2000; Baker et al., 1998; Kuo and Lotse, 1972; Cole et al.,
1953; Griffin and Jurinak, 1973).
19
Freeman and Rowell (1981) studied the adsorption and precipitation of phosphate onto
calcite and concluded that the reaction product of solution phosphate and calcite is a
calcium phosphate. Au1enbach and Meisheng (1988) studied the mechanisms of
phosphorus remova1 from treated wastewater by sand from a sewage treatment system
that had a coating primarily of precipitated CaC03. It was concluded that CaC0
3
can
remove phosphorus from solution by coprecipitation or chemical reaction forming
insoluble calcium phosphates. Baker et al. (1998) conducted phosphorus-sorption
experiments on high calcium limestone and concluded that limestone contributes
significantly to phosphate attenuation. Cole et al. (1953) reported that when phosphate-
containing solutions are placed in contact with particles of calcium carbonate, phosphate
is rapidly removed from solution by the solid particles. According to Cole et al. (1953)
the reaction of phosphate with calcite surfaces initially involves adsorption of small
amounts of phosphate followed by precipitation of calcium phosphate. Brix et al. (2000)
studied the phosphorus-binding capacity of calcite. The results showed that calcite had a
high phosphorus-sorption capacity. It was suggested that a separate unit containing calcite
be constructed as a polishing step where the calcite would be replaced when the
phosphorus-binding capacity was exhausted.
2.5.2.3 Shale
Shale is a soft, finely stratified rock that splits easily into very thin laminae. It is derived
from the lower limestone group of the carboniferous system, consisting of consolidated
mud or clay. Due to the presence of iron, aluminium, and calcium, both adsorption and
precipitation with phosphorus are the mechanisms for phosphorus removal in shale.
Drizo et al. (1997) studied the phosphorus-removal capacity of shale. Virtually complete
removal (98%) of phosphate was achieved over the entire period of investigation
(300 days), with an influent phosphorus concentration of lOto 20 mg L,l. Drizo et al.
(1999) studied substrates that would enhance phosphate removal from wastewater. Shale
showed the greatest mean phosphorus adsorption of seven different substrates. Batch
experiments were used to determine the phosphorus-sorption capacity of the materials. It
20
was suggested that full-scale and supplementary tests were necessary to allow for the
prediction of the life-expectancy of shale as a substrate in a phosphorus adsorption filter.
2.6 Summary of Literature Review
The contamination of water systems with pathogens and the eutrophication of surface
waters has highlighted a need for a wastewater treatment system which will reduce
pollutants to levels whereby they may safely be discharged to receiving waters. Small
rural communities, with limited resources, require wastewater treatment technologies
which are low cost and easily maintained. Constructed wetlands may prove to be an
economical, low maintenance, natural solution with the added benefits that they are
aesthetically pleasing and provide a habitat for wildelife. Numerous studies have shown
constructed wetlands to be effective at reducing BD, SS, P, N and pathogens. However,
their ability to remove phosphorus from wastewater decreases as the system becomes
saturated with the nutrient. A post-wetland phosphorus polishing step may therefore be
required. Two potential phosphorus polishing steps include vegetated filter strips and
phosphorus adsorption filters.
Therefore, this study was initiated in order to determine the treatment capacity of a
constructed wetland and the efficiency of phosphorus adsorption filters and vegetated
filter strips as phosphorus polishing steps.
21
3. MATERIALS AND METHODS
The study was divided into two sections. The first section inc1uded field studies
conducted on the Alfred Municipal Wetland from May to November 2000. This section
of the study sought to examine the treatment capability of the constructed wetland system.
The second area of research consisted of laboratory studies on various phosphorus
adsorption media, conducted from August 2000 to April 2001. The laboratory studies
were conducted at the Research in Transfer Technology Sector of Alfred College of the
University of Guelph.
3.1 Site Description
An experimental wetland system has been constructed to treat the effluent from existing
sewage lagoons in the Village of Alfred, Ontario (population 1,100). The village's
municipal wastewater is currently treated by a two-cell sewage lagoon that discharges
once a year, in the spring, to the Azitica Brook, which eventually discharges to the
Ottawa River north of the village. With the increased quantity of streamflow in the spring
due to snowmelt, the lagoon effluents are diluted such that the pollutant loads comply
with discharge criteria. The lagoon cells were constructed in the early 1970s and are
estimated to surpass their design capacity within five years, inhibiting further population
growth or expansion of local agrifood industries. A wetland system may act as a
secondary treatment step, lowering the lagoon effluents pollutant levels sufficiently that
they may be discharged to the Azitica Brook on a continuaI basis during the spring,
summer and fall months. The Ontario Ministry of the Environment has set the maximum
permissible levels for direct discharge to the Azitica Brook as TN < 3.0 mg L-
1
, TP <
0.3 mg L-' and BOD < 0.3 mg L-' (Ontario Ministry of the Environment, 1999). If the
pilot-scale experimental constructed wetland is a success, then a full-scaie wetland system
will be constructed to treat the lagoon effluent year-round.
The experimental constructed wetland system, consisting of a free-surface wetland and
two post-wetland polishing steps (a vegetated filter strip and phosphorus adsorption
filters) has been designed to treat 5-15% (approximately 155 m
3
dai') of the flow
22
entering the Alfred municipal sewage lagoons. The wetland system was constructed in the
summer of 1998 and began operation in the fall of 1999. Figure 3.1 is an aerial
photograph of the site.
The constructed wetland is a free-surface three-cell wetland system, following a marsh-
pond-marsh design (Figure 3.2). The first and third cells, FSW 1 and FSW II,
respectively, are shallow basin surface-flow wetlands, operating at a water depth between
10-20 cm. These cells contain densely growing emergent plants, predominantly cattails
(Typha latifolia) with scattered bulrushes (Scirpus acutis) along the borders. The inlet to
FSW 1 is designed to increase aeration of the lagoon effluent. The wastewater enters the
system through a 100 mm PVC gated pipe and is aerated as it flows over a gravel slope.
The second cell is an aerobic basin (AB) which operates at a depth between 60-75 cm.
This cell does not contain any vegetation, which allows for oxygenation to occur at the
air-water interface due to air currents and wind. At lower water depths, anaerobic
conditions exist. The dimensions of the cells are as follows: FSW 1 measures 40 x 78 m;
AB measures 40 x 78 m; FSW II measures 39 x 40 m. A clay liner was added under all of
the wetland cells during the construction phase with the intention of preventing any
leaching of the treated water. Five centimetres of topsoil was placed above the clay liner
as a substratum for rooted plant growth. Water levels are controlled with a stop-log weir
and/or a pivoting outlet pipe. The total retention time of the wetland system is 15 days.
There are two phosphorus polishing steps in the wetland system: a vegetated filter strip
and a set of three slag filters. The vegetated filter strip was established to receive part of
the effluent (39 m
3
dai
1
) from the wetland cells. The three pilot slag filters are used to
test the phosphorus adsorption capacity of blast fumace slag at various phosphorus
concentrations. Three phosphorus concentrations, as depicted in Figure 3.2, will be
considered: 1) effluent discharged directly from the lagoon cells, 2) effluent discharged
from the wetland cells, and 3) effluent discharged from the vegetated filter strip.
23
Figure 3.1 Aerial photograph of the Alfred Municipal Wetland and the municipal sewage lagoons.
Cl) Cl)
Free Surface
~
...
Wetland 1
(FSW 1)
r
1
: Free Surface
......
1
1
..... "'II
1
Wetland 2
Lagoons
Aerobic Basin
1
1
1
1
(FSW Il)
<4l I--Slag Phosphorus
(AB)
1
~
1
...
1
~
Filters
~
1
1
V
1
1 ...... A
1
1
~
l
GW4
Vegetated Filter
Q
Strip
1-
,..
GW2
(VFS)
~
GW1
cv
Figure 3.2 Schematic of the constructed wetland system. Circled numbers identify the
groundwater sampling locations.
During the research period, May to November 2000, aIl of the treated wastewater exiting
the wetland system was retumed to the lagoons. Therefore there was no direct discharge
to surface waters.
3.2 Constructed Wetland System
A sampling of the wetland cells took place in the spring of 2000 to determine the initial
conditions of the wetland, at which time sediment, plant, and water samples were
collected. Water samples were collected twice a month from May through November
2000 at the inflows and outflows of the wetland cells, the vegetated filter strip and the
slag filters to determine each component' s role in nutrient removal. Groundwater
samples were taken once a month to verify that no leaching from the cells was taking
place.
3.2.1 Initial wetland conditions
A sampling of the wetland took place on June 23, 2000, before the treatment season
began. Prior to the sampling, the wetland had functioned for a period of three months in
the fall of 1999. Therefore, the initial conditions will be viewed as background levels.
The pumps were activated June 24, 2000. Figure 3.3 demonstrates the dimensions of the
divided cells and the sample locations. The FSW 1 and AB were each divided into four
quadrats lengthwise, which were then divided into three sub-p10ts across each quadrat's
width. FSW II was divided into two quadrats, each with three sub-plots. Samples of
sediment, plant, and water were taken in the centre of each sub-plot in FSW 1and FSW II.
On1y water samples were taken in AB.
3.2.1.1 Sediment sampling and analysis
Bottom sediment samples were collected from each sampling point using a spade to
scrape the top layer of the sail, and placed in sterile plastic bags. The sterile bags were
placed in freezer zip-Iock bags and frozen until the time of analysis. Samples were
ana1ysed for TN, N03-N, NH4-N, TP and Mehlich P, where Mehlich Pis an analysis used
to determine available phosphorus. The analysis was performed by the Department of
Natural Resource Sciences, McGill University. TN was analysed using the McGill and
26
78 m
1 13 m 1 14 m 1 13 m 1
... ~ . . . ~ . . . ~
18: 17: 16
1 1
Aerobic
Basin
13 : 14 i 15
1 .
1
1
1 1
--------T----------,---------
1 1
1 1
1 1
1 1
1 1
12: 11 : 10
1 1
1 1
1 1
--------T----------,---------
1 1
1 1
1 1
7 : 8 : 9
1 1
1 1
T
20m
t
20m
t
20 m
{-
18 m
t
1 13 m 1 14 m 1 13 m 1
... ~ . . . ~ . . . ~
, i , ,
21 : 20 : 19
1 1
Free-Surface
Wetland 1
22 ! 23: 24
1
1
1
1 1
--------T----------,---------
1 1
1 1
1 1
1 1
27 : 26 : 25
1 1
1 1
1 1
1 1
--------T----------,---------
1 1
1 1
1 1
28 : 29 : 30
1 1
1 1
78 m
6
i 5
1
1
1 4
lm rU)
Free-Surface
Wetland Il
i
2
,
1
3
20m
t
20m
~
1'" ~ I ' " ~ I ' " ~ I
13 m 13 m 13 m
Figure 3.3 Schematic of sampie locations of the initial wetland conditions sampling.
Numbers identify sample locations within each subplot, and are on the centres of the subplots.
Figueiredo (1993) method, in which a soil sample is digested using a digestion mix
composed ofK
2
S0
4
, CUS04 and Se (ratio of 100:10:1) and H
2
S0
4
at 350C for 3 h. The
volume is made to 100 mL and the solution measured colorimetrically for N. N0
3
-N and
NH
4
-N were analysed using the Maynard and Kalra (1993) method, in which a 2 M KCI
extraction is done using a ratio of 1:10 soil-to-solution and shaken for 1 h. The filtrate is
analysed by colorimetric determination for ammonium-N and nitrate-No TP was analysed
using the procedure of Parkinson and Allen (1975), in which the sediments are digested in
sulfuric acid and peroxide with the addition of catalysts (lithium and selenium) at 340C
for about 3 h. The content is diluted to 100 mL and analysed colorimetrically for
phosphorus. Mehlich P was analysed using the Tran et al. (1993) method, a multi-element
extraction using the Mehlich III solution (a mixture of acetic acid, ammonium nitrate,
ammonium fluorid, nitric acid and EDTA).
3.2.1.2 Plant sampling and analysis
Two representative cattails, including both the aboveground portion and roots, were
removed from each sampling point in FSW 1 and FSW II. The samples were placed in a
plastic bag to transport to the laboratory. The biomass was rinsed with tap water to
remove any soil. The plants were then oven-dried to constant mass in an oven-drier at
90C, and stored in paper bags until analysis. In preparation for analysis, the entire plant
biomass was ground to a fine powder. The samples were analysed for total phosphorus
and total nitrogen. The tissues were analysed by the Department of Natural Resources
Science, McGill University using the procedure of Parkinson and Allen (1975), in which
the tissues are digested in sulfuric acid and peroxide with the addition of catalysts
(lithium and selenium) at 340C for about 3 h. The content is diluted to 100 mL and
analysed colorimetrically for nitrogen and phosphorus.
3.2.1.3 Water sampling and analysis
Water samples were collected in 200 mL plastic bottles at each sampling point. The
samples were preserved with 1 ml of 5N sulfuric acid and refrigerated until the time of
analysis. The samples were analysed for N03-N, NH4-N, TKN, and TP. N03-N, NH
4
-N,
and TP were analysed by the Department of Natural Resources Science, McGill
28
University. TKN was analysed by Accutest Labs ofNepean, Ontario. N03-N and NH
4
-N
were analysed using the QuickChem Method (Lachat Instruments,2001), in which the
ammonium of the solution is heated with salicylate and hypochlorite in an alkaline
phosphate buffer. The green colour is measured colorimetrically at 660 nm on a flow
injection instrument. TP was analysed using Technique number CPQ 104E2
(Environment Canada, 1994), in which persulfate is added to the solution to oxidise the
organic phosphorus and the solution is digested in an autoclave. The digested solution is
analysed on the flow injection instrument at 880 nm following a complexation with
ammonium molybdate. TKN was analysed using Standard Methods (APHA, 1989)
macro-Kjeldahl method.
3.2.2 Bimonthly water sampling and analysis
Water samples were collected twice a month from May 19 to November 3, 2000 at the
inflow and outflow of each cell, the vegetated filter strip and the slag filters to determine
each one's role in nutrient removal. The samples were analysed for BOD
s
, nitrate and
nitrite, ammonium and ammonia, TKN, SS, TP, ortho-P0
4
, fecal coliforms and E.coli.
The analysis was done by Accutest Labs of Nepean, Ontario. The methods used for the
analysis were as follows: BOD
s
was analysed fol1owing the methodology outlined in
Standard Methods (APHA, 1989); nitrate/nitrite and ammonialammonium were analysed
by the Standard Methods' (APHA, 1989) method using an ammonia selective electrode;
TKN was analysed using the macro-Kjeldahl method (APHA, 1989); SS was analysed
using the methodology outlined by Standard Methods (APHA, 1989); the methodology
followed for the analysis of TP first converts all of the phosphorus into orthophosphates
using an acid digestion, and then the automated ascorbic acid method was implemented
(APHA, 1989); ortho-P0
4
was analysed by the automated ascorbic acid method (APHA,
1989); fecal coliform was analysed fol1owing the methodology outlined in Standard
Methods (APHA, 1989); and E. coli was analysed fol1owing the methodology outlined in
Standard Methods (APHA, 1989).
29
3.2.3 Monthly groundwater sampling and analysis
Groundwater samples were taken at four locations surrounding the Alfred Municipal
Wetland once a month from May to November 2000. The sample locations referred to as
GWI, GW2, GW3 and GW4 are identified in Figure 3.2. The samples were analysed for
BOD
s
, NH
3
-N, N03-N, TSS, TP, O-P0
4
, fecal coliform and E. coli. The analysis was
done by Accutest Labs of Nepean, Ontario and analysed using the same methodology as
described above for the bimonthly water sampling.
3.3 Phosphorus Polishing Step
3.3.1 Media for phosphorus removal
Short-term shaker experiments were used as an efficient method of companng
phosphorus removal rates of the three reactive materials selected for study: blast furnace
slag, shale and calcite. In addition to the shaker tests, column experiments were
conducted to assess the long-term phosphorus removal capacities under conditions of
continuous phosphate loading. The results of this study would aid in the selection of a
material to incorporate in the design of a phosphorus filter.
3.3.2 Description of soil materials
The three materials chosen for investigation were:
Blast furnace slag (BFS), a calcium-aluminium silicate by-product of iron
production, consisting of high Al and Fe concentrations. The BFS used in this
study was obtained from International Mills Services of IVACO in L'Orignal,
Ontario.
Shale, a soft, finely stratified rock that splits easily into very thin laminae,
consisting of Fe, Al, and Ca. The one used in this study was obtained from
Lalonde Carrire in Alfred, Ontario.
Calcite, ninety-nine percent calcium carbonate, was obtained from OMYA, St-
Armand, Quebec.
30
The pH of each substrate was measured in a 1:2.5 (w/v) substrate/water mixture after
equilibrating for 24 hours using a gel tip electrode (n=3), as outlined by Sakadevan and
Bavor (1998). The bulk density (g cm-
3
) was based on the ratio between the dry weight
and the bulk volume of the medium (n=3). Porosities were determined by the amount of
water needed to saturate a known volume of medium (n=3). The slag, shale, and calcite
ranged in particle size from 4.75-25.40 mm, 4.75-38.10 mm, and 6.35-19.05 mm,
respectively.
3.3.3 Phosphate adsorption measurement
The procedure used for the phosphate adsorption measurement was adapted from the
methods used by Sakadevan and Bavor (1998). Ten grams of dry solids (n=3) were
equilibrated in a 250 mL Erlenmeyer glass flask with 100 mL of O.OlM potassium
chloride solution containing concentrations of 0.5, 1.0, 3.0 and 5.0 g L-
1
K
2
HP0
4
, except
for slag, which was tested with 0.5 and 5.0 g L-
1
K
2
HP0
4
. The flasks were shaken in a
horizontal shaker at a rate of 1000 rpm for 48 hours. An aliquot of the supernatant was
filtered through 1.5 Ilm Whatman microfibre filters and after adequate dilution, the
phosphate content of the supernatant was determined by the use of the Standard Test
Methods for Phosphorus in Water - Orthophosphate Method (ASTM 515-88). The
phosphate that disappeared from the solution was assumed to have been removed by the
medium in question. The Langmuir and Freundlich equations were then used to interpret
the equilibrium data. The experiments were conducted at room temperature. A second
unfiltered aliquot was used for measurement of pH.
During the course of the study, additional shaker experiments on the three substrates were
deemed necessary. Shaker experiments were conducted on the substrates with particle
sizes ranging as follows: slag from 4.75-25.40 mm, calcite from 0-6.35 mm and
6.35-19.05 mm, and shale from 0-4.75 mm and 4.75-38.10 mm. Forty grams of dry solids
were equilibrated in a 500 mL Erlenmeyer glass flask with 400 mL of O.OlM KCl
solution containing a concentration of 15 mg L-
1
K2HP04. The solutions were sampled at
4,8,24 and 48 hours (n=3). Measurements ofpH were taken at each sampling period.
31
3.3.4 Column experiments
Large-scale columns were constructed In order to study the long-term phosphorus
removal capacity of the materials. Twelve acrylic columns (inner diameter 15 cm; height
210 cm) were packed to a height of 120 cm with each of the three substrates. The
columns were placed on a horizontal wooden platform and were secured by attaching
them to a metal frame. Ports were created at 30 cm vertical intervals for the monitoring of
effluent water with depth. Each port had a tube leading upward to test for constant head.
A head loss would imply the formation of capillaries. A head gain would signify plugging
of the media. Each column was intermittently dosed from above with a synthetic waste
water solution of K
2
HP0
4
from varying reservoirs. Intermittent delivery was chosen as
this reflects what is often the case when pretreated wastewater is discharged into
constructed wetland systems (Johansson, 1999). Separate peristaltic pumps for each
column operated for an average of 2-minute periods, six times an hour, supplying an
average of 33 L dai
1
The columns were run under saturated water conditions, as the
effluent levels of the columns were set just above the surface of the medium in the
columns. The outflow was controlled by gravity. A tube exiting the bottom of the column
was run up the height of the column to the desired level of water in the column, and then
allowed to overflow. The columns consisted of an overhead flow which would prevent
overflowing of the columns in case of plugging. A schematic of the column set-up is
shown in Figure 3.4
A phosphate breakthrough experiment was conducted for each column. An influent
solution was prepared by dissolving reagent-grade K
2
HP0
4
salt in tap water. Samples of
the outflow from each port of each column were taken an average of twice a week, in
200 mL plastic bottles. The samples were measured for pH and analysed for phosphorus
content, using the Standard Test Methods for Phosphorus in Water - Orthophosphate
Method (ASTM 515-88). The samp1es were refrigerated at 4C unti1 ana1ysis. The amount
of sorbed phosphate was calculated from the difference between the phosphate
concentration in the initial solution and in the effluent sample.
32
P-solution
Water level
l Port 1
Substrate
Overflow outlet
Effluent outlet
30 cm
30 cm
30 cm
Port 2
Port 3
Port 4
E
()
o
C'\I
..-
E
()
o
..-
C'\I
10lil ~ I
15 cm
Figure 3.4 Schematic of the column set-up.
The total concentration of phosphorus in an ordinary domestic wastewater is within the
range of 6-20 mg Cl (Kadlec and Knight, 1996). Based on this range, 15 mg L-
I
of
phosphate was selected as the influent concentration for the slag, shale and calcite
columns. However, in an attempt to simulate the conditions of the wetland wastewater
treated by the current slag filter, an additional set of slag columns was constructed with an
influent phosphate concentration of 2 mg L-
I
. These four treatments were run in triplicate
giving a total of 12 columns. The 12 columns were designated as follows: three columns
were filled with slag to be fed a concentration of 2 mg P0
4
L-
I
(SL2-l, SL2-2, SL2-3).
The remaining columns were fed a concentration of 15 mg P L-
I
. Three columns were
filled each with slag (SL15-l, SL15-2, SL15-3), shale (SH15-l, SH15-2, SH15-3), and
calcite (CA15-l, CA15-2, CA15-3). A photograph of the experimental column set-up is
shown in Figure 3.5.
Columns SL2-l, SL2-2 and SL2-3 began running on August 15, 2000 at an influent
phosphate concentration of 2 mg P0
4
L-
I
. In an attempt to achieve saturation in these
columns, the phosphate concentration was increased to 5 mg P0
4
L-
I
on November 14,
2000. Columns SL15-l, SL15-2, SL15-3, SH15-l, SH15-2, SH15-3, CA15-l, CA15-2
and CA15-3, began running November 22, 2000, with an influent phosphate
concentration of 15 mg P04 L-
I
. The average retention time for each column was eight
hours, equivalent to flow rates of 1.59, 1.31 and 1.53 L h-
I
for slag, calcite and shale,
respectively.
34
s
c
Q)
E
'i:
Q)
C.
><
Q)
c
E
::::s
'0
u
...
oS
c.
::::s
..:.
Q)
tn
S
C
Q)
E
'i:
Q)
C.
><
w
LI)
C")
e
::::s
C)
u.
4. RESULTS AND DISCUSSION
4.1 Initial Wetland Conditions
This section presents results from the wetland sampling conducted to determine the
background levels of nitrogen and phosphorus in the Alfred Municipal Wetland which
took place on June 23, 2001. The nitrogen and phosphorus concentrations of the
sediment, plant and water samples are presented in Appendix A.
4.1.1 Sediment samples
The mean total nitrogen sediment concentration was higher in FSW 1 (1698 mg kg-
l
) than
in FSW II (1154 mg kg-
l
) (Figure 4.1). The mean ammonium-nitrogen concentration was
12.9 mg kg-
l
in FSW 1and increased to 20.8 mg kg-
l
in FSW II (Figure 4.1). The mean
nitrate-nitrogen concentration was 0.3 mg kg-
l
in FSW 1and decreased to 0.1 mg kg-
l
in
FSW II (Figure 4.1).
The mean total phosphorus concentration was 10wer in FSW II (721 mg kg-
l
) than in
FSW 1 (802 mg kg-
l
) (Figure 4.1). The mean Mehlich phosphorus was higher in FSW 1
(10.7 mg kg-
l
) than in FSW II (2.5 mg kg-
l
) (Figure 4.1). Similar to this study, Gale et al.
(1994) reported greater concentrations of phosphorus in the first of two wetland cells
constructed in series receiving wastewater.
The nitrogen and phosphorus leve1s in the sediments being higher in FSW 1than in FSW
II may be attributed to the higher concentrations of the nutrients in the wastewater in
FSW 1 than in FSW II. It is possible that with lower nutrient concentrations in the
wastewater, fewer nutrients are available to be sorbed by the sediments.
Adcock et al. (1995) performed a nutrient partitioning study on a free-surface wetland in
Sydney, Australia. The wetland was three years old at the time of the study, and, similar
to the Alfred Municipal Wetland, had relatively low nutrient influent concentrations. The
mean TN and TP sediment concentrations were 1,330 mg kg-
l
and 1,165 mg kg-l,
respectively. These values are comparable to the sediment concentrations determined in
36
(a) Mean sediment total phosphorus and total nitrogen
-C)
~ 2000
E
-
z 1500
1-
"C
s:::
1000
C'CI
0..
1-
...
500
s:::
(\)
E
"C
0
(\)
U)
FSWI FSW Il
Wetland CeIls
(b) Mean sediment nitrate-nitrogen, ammonium-
nitrogen and Mehlich phosphorus
FSWI
~ 25
"lt_
:I: C)
Z ~ 20
ft C)
~ .. 15
00..
Z oC 10
... 0
s:::=
(\) oC 5
.5 ~
-g 0 +------
U)
Wetland CeIls
FSW Il
N03-N
IBNH4
o Mehlich P
Figure 4.1 Mean sediment concentrations in FSW 1and FSW Il of the Alfred
Municipal Wetland.
this study. Although the sediment TN and TP contents determined by Adcock et al.
(1995) were higher than those of this study, it is possible that the difference may be
attributed to the fact that the wetland of the CUITent study has not been operating as long,
and therefore has not had as long a period to sorb as much nutrients.
4.1.2 Plant samples
Higher total nitrogen and total phosphorus tissue contents were recorded In FSW 1
(TN=10,351 mg kg-
I
and TP=1,262 mg kg-
I
) and dec1ined In FSW II
(TN=9,460 mg kg-
I
and TP=1,004 mg kg-
I
) (Figure 4.2).
Adcock et al. (1995) reported a similar trend of phosphorus and nitrogen tissue contents
being highest c10sest to the influent source and decreasing with distance from the source
in a constructed wetland treating wastewater. Adcock et al. (1995) conc1uded that these
differences suggest that the plants, throughout the wetland, are not accessing nutrients
from the sediments, and therefore must be removing the nutrients from the wastewater.
4.1.3 Water samples
The measured influent value of ammonium-nitrogen in FSW 1 a few days prior to and
following the wetland sampling, as recorded by the bimonthly water samples, was
0.21 mg L-
I
on June 16,2000 and 0.22 mg L-
I
on June 30, 2000. The FSW 1reduced the
influent to a mean value of 0.17 mg L-
I
. The mean ammonium-nitrogen concentration
was reduced further in AB (0.08 mg L-
I
) and FSW II (0.04 mg L-
I
) (Figure 4.3). The
continued reduction of ammonium-nitrogen with distance from the influent source may
be an indication that nitrification is taking place in all three cells. This was anticipated as
nitrification will occur in an aerobic environment, as exists in FSW l, AB and FSW II
(Kadlec, 1995). It is also possible that rather than nitrification removing the ammonium-
nitrogen from the wastewater, plant uptake may have been responsible for the
ammonium-nitrogen removal. Plants that grow in waterlogged soils in which ammonium
levels are high, use ammonium much more efficiently than nitrate-nitrogen (Nichols,
1983). However, although plant uptake may have contributed to the removal of
ammonium-nitrogen in FSW 1 and FSW II, there were no emergent plants and few
38
Mean plant total phosphorus and
total nitrogen
-
~ 12000
-
~ 10000
-
z 8000
....
"tJ 6000
c
:. 4000
.... 2000
-
c
eu 0 +--
a::
FSWI
Wetland Cells
FSW Il
Figure 4.2 Mean plant tissue concentrations in FSW 1 and FSW Il of the
Alfred Municipal Wetland.
(a) Mean water total phosphorus,
ammonium-nitrogen and nitrate-nitrogen
N03-N
mNH4
DTP
FSW Il AB
Wetland CeIls
FSWI
0.150
0.000 +---'-
0.200
Z
1
"lit
:J:
Z
Z
1 _
M-I
~ ~ 0.100
0:-
1- 0.050
(b) Mean water total Kjeldahl nitrogen
2.5
::i
C, 2
E
i' 1.5
~ 1
...
~ 0.5
o
FSWI AB
Wetland Cells
FSW Il
Figure 4.3 Mean water concentrations in FSW l, FSW Il and AB of the Alfred
Municipal Wetland.
submergent plants growmg m AB, although AB contributed to further reduction of
ammonium-nitrogen. Therefore, it is likely that nitrification played a greater role than
plant uptake in the removal of ammonium-nitrogen from the wastewater.
The influent nitrate-nitrogen concentration of FSW 1 was less than 0.1 mg LoI a few days
prior to and following the wetland sampling. The mean nitrate-nitrogen concentrations
were low throughout the wetland cells, reduced to less than 0.005 mg L-
I
(Figure 4.3).
There are two possible explanations for the low levels of nitrate-nitrogen in the water.
The nitrates produced by nitrification may have been denitrified to nitrogen gas, nitrous
oxide or nitric oxide once anaerobic conditions were present, as in the lower depth of the
water column of AB (Home, 1995). It is also possible that rather than nitrification
removing the ammonium from the wastewater, plant uptake may have been responsible,
in which case additional nitrate-nitrogen was not produced as a result of nitrification.
These hypotheses may explain the nitrate-nitrogen concentrations remaining low.
According to Home (1995) it is unlikely that nitrate-nitrogen was removed by plant
uptake since the macrophytes have their roots in the soil and therefore remove little
nitrate-nitrogen from surface water directly.
The measured influent values of total Kjeldahl nitrogen to FSW 1 on June 16, 2000 was
1.69 mg L-
I
and 2.00 mg L-
I
on June 30, 2000. Total Kjeldahl nitrogen was reduced from
a mean concentration of 2.01 mg L-
I
in FSW 1 to 0.63 mg L-
I
in AB and then increased
slightly to 0.81 mg L-
I
in FSW II (Figure 4.3).
According to Brix (1994), total nitrogen removal in free-surface wetlands is often greater
than 50%. Although total nitrogen was not directly measured in the wetland samples,
looking at the different nitrogen components that were analysed (N03-N, NH
4
-N, TKN),
the concentrations of each parameter were reduced by more than 50%, referring to the
influent concentrations to FSW 1as initial concentrations.
The measured influent values of total phosphorus to FSW 1 on June 16, 2000 was
0.52 mg L-
I
(no value was measured for June 30, 2000). The mean total phosphorus
41
concentration was reduced by FSW 1 to 0.16 mg L-
1
This value decreased to 0.03 mg L-
1
in AB and then increased slightly to 0.04 mg L-
1
in FSW II (Figure 4.3). Richardson
(1985) reported that rooted emergent wetland vegetation removes substantial quantities of
phosphorus' from wastewater. The results from the phosphorus analysis in the wetland
plant tissues, where plant tissues in FSW 1 contained higher phosphorus concentrations
than in FSW II, as weIl as Richardson's reports that phosphorus in wastewater is removed
by wetland vegetation, suggests that the vegetation in the Alfred Municipal Wetland is at
least partiaIly responsible for the reduction of phosphorus in the wastewater. According to
Mann (1990) the substrate may play the greatest role in phosphorus removal in wetlands.
As with the plant tissues, the phosphorus levels in the sediments in FSW 1 were higher
than in FSW II. This suggests that the sediments were sorbing phosphorus from the
wastewater. Therefore, it is believed that both plant uptake and sediment adsorption
contributed to the removal of phosphorus from the wastewater.
4.2 Bimonthly Water Sampling
This section presents results from the bimonthly water samples taken at the inlet and
outlet of each wetland ceIl as weIl as the slag filters and vegetated filter strip during the
sampling period from May 19 to November 3,2000.
4.2.1 Constructed wetland cells
Since the village of Alfred has a primary wastewater treatment with the lagoon ceIls, the
nutrient concentrations entering the wetland are relatively low, as shown in Table 4.1.
Dilution effects were not considered in the overaIl removal of poIlutants.
Table 4.1 Average influent pollutant concentrations to FSW l, May 19 to November
3,2000 (n=13, except TSS n=12,TP n=8, O-P04 n=6).
E. coli Fe BOD
5
TKN NH
4
-N N0
3
-N TSS TP 0-P0
4
(count (count (mg L'1) (mg L'1) (mg L'1) (mg L'1) (mg L'1) (mg L'
1
) (mg L'1)
100mL
1
) 100mL-
1
)
64.85 82.77 3.62 1.67 0.11 <0.10 82.67 0.33 0.18
As shown in Table 4.1, the average influent concentration of N0
3
-N is below the
detection limit 0.1 mg L-
1
) and remained so at aIl stages of the wetland system
throughout the period of study. Since this concentration is below the maximum
42
permissible levels for discharge, nitrate-nitrogen is not a concern and this constituent will
not be discussed further.
The influent and effluent concentrations from different stages in the Alfred Municipal
Wetland at each sampling date from May 19 to November 3, 2000 are presented in
Appendix B. The removal of pollutants is summarized for aIl of the treatment stages in
Table 4.2, averaged over the period from May 19 to November 3, 2000. As shown in
Table 4.3, the pollutants are reduced by 34-93% in concentration by the wetland cells
FSW l, AB and FSW II.
It can be seen from Table 4.3 that the TN, TP and BOD
s
are reduced to below the
maximum acceptable discharge levels (TN < 3 mg L-
1
, TP < 0.3 mg L-
1
, BOD
s
<
3 mg L-
1
) by the three wetland cells. Therefore, if the wetland cells continue to perform at
this level, continuaI discharge from the wetland may be a solution to the village's
problem of the wastewater exceeding the capacity of the lagoons.
Outflow densities of fecal coliforms have been monitored at a number of pilot and full-
scale wetland treatment systems and have been summarized by Kadlec and Knight (1996)
for sorne of the wetland systems receiving municipal wastewater. The fecal coliform
count in the influent and effluent of the wetland systems ranged from 239 to over
1,000,000 coliforms per 100 mL and from 10 to 4,000 coliforms per 100 mL,
respectively, representing reductions of 85 to 99.9%. The reduction of fecal coliforms by
the Alfred Municipal Wetland was approximately 52%. The lower reduction may be a
result of the low influent value of 82.77 counts per 100 mL. Kadlec and Knight (1996)
report that bacterial removal efficiency in wetlands is a function of the inflow bacteria
population, stating that removal efficiency is typically high at high inflow populations,
but declines when inflow populations are lower.
43
Table 4.2 Summary ofmean performance of the Alfred Municipal Wetland from May 19 to November 3,2000.
FSWI AB FSWII Slag l Slag 2 Slag 3 VFS
BOD
s
Influent concentration, mg L-
I
3.62 3.5* 2.54 2.1 1.85 U NIA NIA NIA 2.38 1.8
Effluent concentration, mg L-
I
2.54 2.1 1.85 1.1 2.38 1.8 NIA NIA NIA 1.85 1.0
Percent removal 23.00 32.5 18.60 29.7 3.08 lU NIA NIA NIA 18.32 29.1
TKN
I
1.67 0.6 0.91 0.18 0.81 0.3 NIA NIA NIA 1.05 0.5
I
0.91 0.2 0.81 0.30 1.05 0.5 NIA NIA NIA 0.98 0.4
Percent removal 41.22 16.5 17.48 15.8 0.05 3.4 NIA NIA NIA 10.90 17.9
NH
4
-N
I
0.11 0.04 0.06 0.03 0.06 0.03 NIA NIA NIA 0.05 0.02
I
0.06 0.03 0.06 0.03 0.05 0.02 NIA NIA NIA 0.03 0.008
NOrN
I
< 0.1 0.0 < 0.1 0.0 < 0.1 0.0 NIA NIA NIA < 0.1 0.0
I
< 0.1 0.0 < 0.1 0.0 <0.1 0.0 NIA NIA NIA < 0.1 0.0
TSS
I
82.67 60.4 17.50 8.3 5.4 O 2.6 NIA NIA NIA 6.182.04
I
17.50 8.3 5.4 O 2.6 6.182.04 NIA NIA NIA 15.92 8.3
Percent removal 42.36 22.5 53.2 O 19.6 11.7 10.5 NIA NIA NIA 21.50 17.0
TP
I
0.33 0.2 0.04 0.02 0.03 0.009 0.91 0.3 0.03 0.01 0.05 0.03 0.03 0.01
I
0.04 0.02 0.03 0.009 0.03 0.01 0.03 0.01 0.01 0.0 0.01 0.00 0.05 0.03
Percent removal 49.46 34.6 27.78 23.3 4.76 9.3 99.40 0.7 54.05 24.2 59.21 26.9 4.76 9.3
O-P04
I
0.180.23 0.03 0.006 0.03 0.01 1.79 0.9 0.03 0.02 0.04 0.02 0.03 0.02
I
0.03 0.006 0.03 0.01 0.03 0.02 0.02 0.02 0.01 0.00 0.01 0.00 0.04 0.02
Percent removal 31.25 37.6 0.00 0.00 10.00 19.6 92.67 10.2 58.73 23.8 62.04 25.5 0.00 0.00
Fe
1
82.77 41.5 33.62 27.1 31.85 12.1 NIA NIA NIA 39.58 24.6
I
33.62 27.1 31.85 12.1 39.38 24.6 NIA NIA NIA 30.62 16.6
Percent removal 41.76 25.7 13.79 16.9 17.2 O 12.5 NIA NIA NIA 28.20 20.7
E. coli
I
64.85 28.9 25.69 19.9 26.46 9.8 NIA NIA NIA 26.92 17.9
1
25.69 19.9 26.46 9.8 26.92 17.9 NIA NIA NIA 18.62 9.0
*95% confidence intervals indicated
Table 4.3 Average concentrations at the inlet and outlet of the wetland cells from
May 19 to November 3, 2000.
Parameter Average Standard Deviation
BOD
s
(mg l-1) ln 3.62 3.50
Out 2.38 1.76
% Removal 34.00
TKN (mg l-1) ln 1.67 0.58
Out 1.05 0.54
% Removal 37.30
NH
4
-N (mg l-1) ln 0.11 0.08
Out 0.05 0.03
% Removal 51.72
TSS (mg l-1) ln 82.67 106.74
Out 6.18 67.58
% Removal 92.52
TP (mg l-1) ln 0.33 0.34
Out 0.03 0.02
% Removal 89.89
0-P0
4
(mg l-1) ln 0.18 0.28
Out 0.03 0.02
% Removal 81.82
Fe ln 82.77 76.39
(counts 100 ml-
1
) Out 39.38 45.34
% Removal 52.42
E.coli ln 64.85 53.15
(counts 100 ml-
1
) Out 26.92 33.01
% Removal 58.48
The wetland cells reduced E. coli levels by 58%. Schreijer et al. (1997) reported E. coli
removal of 90% by a free-surface wetland, with influent counts of 30,000 per 100 mL. A
similar argument may be used to explain the lower performance of the wetland cells at
reducing E. coli as that used to explain the lower reduction of fecal coliforms. The
influent levels of E. coli were relatively low (65 counts per 100 mL), and according to
Kadlec and Knight (1996), the removal efficiency of wetlands declines when inflow
populations are lower.
4.2.2 Vegetated flUer strip
The vegetated filter strip treated wastewater discharged from the constructed wetland. It
did not contribute to a significant reduction of TP or O-P0
4
levels (Table 4.2 and
Appendix B). Research reported by Uusi-Kamppa et al. (2000) on numerous vegetated
filter strips showed total phosphorus removal ranging from 27 to 97%. It is possible that
the filter strip in the CUITent study did not produce similar results due to the influent
phosphorus concentrations to the filter strip being very low (TP = 0.03 mg L-
I
and O-P04
45
= 0.03 mg L-
I
). Therefore, unless the influent concentrations were to increase from the
wetland cens, it is not necessary to have the vegetated filter strip as a phosphorus
polishing step as part of the Alfred Municipal Wetland.
However, the vegetated filter strip did contribute to the reduction ofBOD
s
, TKN, NH4-N,
TSS, Fe and E. coli concentrations (Table 4.2 and Appendix B). Although the wetland
cens by themselves succeeded at treating these parameters to levels low enough to
discharge directly to the Azitica Brook, if additional polishing was desired, the vegetated
filter strip would contribute to a further reduction ofthese parameters.
4.2.3 Slag filters
The slag filters treated wastewater discharged directly from the lagoon cens (Slag 1), the
wetland cens (Slag 2), and the vegetated filter strip (Slag 3) (Appendix B). The TP
concentrations were reduced by 99.4, 54.1 and 59.2% by Slag 1, Slag 2 and Slag 3,
respectively (Table 4.2). The reason Slag 1 outperformed Slag 2 and Slag 3 is most likely
due to the influent concentration to Slag 1 being much greater (0.91 mg L-
I
) than the
influents to Slag 2 or Slag 3 (0.03 mg L-
I
and 0.04 mg L-
I
). The effluents from the three
slag filters an met the discharge criteria for TP (TP < 0.3 mg L-
I
) required for direct
discharge to the Azitica Brook. Therefore, in terms of treating TP, filtering the effluent
from the lagoon cens with the slag filters is a sufficient treatment following which
discharge to the brook would be permissible. This is an important finding since it is
estimated that after 2-5 years (Drizo et al., 1999) the wetland may no longer be effective
at removing phosphorus from wastewater. Slag filters could be used to remove the
phosphorus from the wastewater, and when the substrate became saturated, the filter
would simply be removed and replaced with a new one.
4.3 Monthly Groundwater Sampling
The four groundwater sampling locations surrounding the Alfred Municipal Wetland are
referred to as GW1, GW2, GW3 and GW4. The results of the groundwater samples are
presented in Table 4.4. In general, the four sampling locations had similar pollutant
46
Table 4.4 ResuUs ofmonthly groundwater samples from June to November 2000.
Date
BOD
5
(mg Loi) TKN (mg Loi) NH
3
(mg Loi)
GW1 GW2 GW3 GW4 GW1 GW2 GW3 GW4 GW1 GW2 GW3 GW4
16-Jun 1 1 1 5 0.59 0.82 0.69 1.13 0.25 0.26 0.08 0.84
19-Jul 5 2 3 2 0.91 1.16 0.86 0.22 0.36 0.20 0.26 0.22
3-Sep 2 3 2 1 0.34 0.44 0.48 0.80 0.06 0.10 0.22 0.38
12-0ct <1 3 <1 4 0.27 0.31 0.35 0.42 0.02 0.09 0.07 0.15
3-Nov <1 2 <1 1 0.32 2.12 0.48 0.43 0.06 0.12 0.20 0.13
Date
N0
3
-N (mg Loi) TP (mg Loi) 0-P0
4
(mg Loi)
16-Jun 0.11 0.12 <0.1 0.48 0.03 0.12 0.06 0.09 NIa NIa NIa NIa
19-Jul 0.16 <0.1 <0.1 <0.1 <0.01 0.05 0.03 <0.01 <0.01 <0.01 <0.01 <0.01
3-Sep <0.1 <0.1 <0.1 0.33 <0.01 0.06 0.03 0.02 0.03 0.18 0.09 0.07
12-0ct 0.12 0.11 <0.1 0.79 <0.01 <0.01 <0.01 <0.01 0.03 <0.03 0.03 0.03
3-Nov <0.1 <0.1 <0.1 0.36 0.04 0.13 0.10 0.05 0.03 <0.03 0.03 0.03
Date
TSS (mg Loi) Fe (counts 100 ml-il E. coli (counts 100 ml-il
16-Jun 3 14 20 40 <10 100 40 <10 <10 50 40 <10
19-Jul 14 156 81 81 <10 <10 20 <10 <10 <10 20 <10
3-Sep 140 130 90 29 0 0 0 0 0 4 0 0
12-0ct NIa NIa NIa NIa <10 <10 <10 <10 <10 <10 <10 <10
3-Nov 90 185 240 12 <10 <10 <10 <10 <10 <10 <10 <10
concentrations. Sampling location GW4 had slightly higher TKN, NH
3
-N and N0
3
-N
concentrations than the other locations. GW4 is located near the lagoon cells. Although
the lagoon cells have a packed clay liner, it is possible that over time nitrogen leached
through the soil profile (Agriculture and Agrifood Canada, 2000a).
Since these data represent the first year that the Alfred Municipal Wetland had functioned
for an entire season, it may be viewed as background pollutant levels. Future data may be
compared against these data to help determine whether the wetland system is contributing
to the contamination of the underlying groundwater.
4.4 Substrate for Phosphorus Adsorption Filters
This section presents results from the laboratory experiments conducted to determine a
material to incorporate in the design of a phosphorus filter.
4.4.1 Description of soil materials
The measured values of the physical-chemical characteristics of the three substrates are
presented in Table 4.5.
Table 4.5 Material characteristics. (Standard deviations are shown in parentheses).
8ubstrate pH Porosity Bulk Density Particle size
(%) (9 1000 ml- ) (mm)
81a9 9.25 (0) 58.8(1.7) 1531.4 (5.8) 4.75-25.40
8hale 8.56 (0) 56.6 (0.3) 1081.8 (18.2) 4.75-38.10
Calcite 8.28 (0) 48.7 (1.8) 1656.9 (19.2) 6.35-19.05
4.4.2 Phosphate adsorption measurement
The shaker results are summarized in Table 4.6. After 48 hours of shaking with 0.5, 1.0,
3.0 and 5.0 g P0
4
L-
I
, slag removed 19-98% of the initial P0
4
, calcite removed between
60-70% and shale removed between 50-69%. 81ag showed the greatest mean phosphate
adsorption (24.22 mg g-I with an initial P0
4
concentration of 5.0 g P0
4
L-
I
) of the three
substrates tested as a function of phosphate concentration in solution, followed by calcite
(6.95 mg g-I with an initial P0
4
concentration of 1.0 g L-
I
) and then shale (6.89 mg g-I
with an initial P0
4
concentration of 1.0 g L-
I
).
48
Table 4.6 Results of shaker experiments run for 48 hours at initial
concentrations of 0.5, 1.0,3.0 and 5.0 g P04 L-
1
% Phosphate removed fram solution

phosphate
P0
4
Cone. (g L-')
0.5
1.0
3.0
5.0
81ag
97.90
n.d.
n.d.
19.39
8hale
49.87
68.90
o
o
Calcite
60.13
69.53
o
o
Calcite and shale were effective phosphate adsorbers at 0.5 and 1.0 g L-
1
, but at the higher
concentrations of 3.0 and 5.0 g L-
1
there was no phosphate removed from the solution.
For this reason the higher concentrations were removed from the calculations when
calcite and shale were fitted to the adsorption isotherms. The correlation coefficients (R
2
)
and constants for the Freundlich and Langmuir isotherms for slag, calcite and shale are
displayed in Table 4.7.
Slag was not weIl modeled by either the Freundlich or Langmuir equation, as per the
correlation coefficients, 0.118 and 0.002, respectively. However, due to the success of
slag as a phosphate adsorber in previous studies, it was decided that the substrate
warranted further study in column experiments.
Table 4.7 Coefficients of Freundlich and Langmuir adsorption isotherms for slag,
shale and calcite.
n K R
2
81ag 8.1 2.41 0.12
Calcite 4.5 1.69 0.80
8hale 4.0 1.34 0.70
8ubstrate Freundlieh
K
1
(mg kg-'*)
519
-148
-81
Langmuir
K
2
0.022
-0.0854
-0.1051
R
2
0.00
0.75
0.40
*mg P0
4
kg-
I
substrate (slag, calcite and shale)
The Freundlich equation modeled the phosphate adsorption data better than the Langmuir
equation for both calcite and shale, with Freundlich correlation coefficients of 0.80 and
0.70, respectively. This agrees with a number of independent observations (Lee et al.,
1996; Sakadevan and Bavor, 1998; Roques et al., 1991; Mann and Bavor, 1993) showing
that the Freundlich adsorption equation explained phosphorus adsorption better than the
Langmuir equation. The Freundlich equation implies that the affinity for adsorption
decreases exponentially with increasing saturation (Kuo and McNeal, 1984). A higher K
49
value equates to greater phosphorus adsorption capacity (Sakadevan and Bavor, 1998).
The larger the n value, the stronger the adsorption bond (Crolla et al., 2000).
The K values are similar in comparison with other Freundlich isotherm constants of
various substrates (Table 4.8), except for those reported by Lee et al. (1996). The dust
slag and cake slag used by Lee et al. (1996) had a much smaller particle size
(approximately 85% less than 0.06 mm in diameter), whereas the particle size of the
calcite and shale used in this study was 6.35 to 19.05 mm and 4.75 to 38.10 mm,
respectively. This may explain the large difference in reported K values between Lee et
al. (1996) and this study.
In the present study, the n values are much lower than those reported by Sakadevan and
Bavor (1998) (Table 4.8). When comparing the chemical characteristics of the slags used
in the studies, the calcium oxide (CaO) levels are similar. However, the iron oxide (FeO)
levels in the steel furnace slag (20-30%) and the aluminium oxide (Ab03) levels in the
blast fumace slag (13-16%) used by Sakadevan and Bavor (1998) are higher than the
levels found in the slag used in this study (approximately 9 and 2% for FeO and Ab03,
respectively).
Table 4.8 Freundlich isotherm constants ofvarious substrates.
Substrate
Dust Slag (Lee et al., 1996)
Cake Slag (Lee et al., 1996)
Steel Fumace Slag (Sakadevan and Baver, 1998)
Blast Fumace Slag (Sakadevan and Baver, 1998)
n
1.13
1.09
218
677
K
261
81.7
2.44
2.23
0.99
0.99
0.77
0.97
Sakadevan and Bavor (1998) found, when studying adsorptive soil substrates, that at
lower initial concentrations (0-200 mg P L-
1
) more than 50% of the applied phosphorus
was adserbed, however, at higher phosphorus concentrations (>200 mg P L-
1
) these
substrates adsorbed less than 30% of the applied phosphorus. It is possible that a similar
trend was observed with the present shaker experiments. Since the phosphorus
concentration in the feeding solution to the columns was to be a much lower
concentration (15 mg P L-
1
), it was suspected that the substrates would perform better in
50
the column studies than in the shaker experiments. In addition, laboratory adsorption tests
are commonly used to estimate the amount of phosphorus that a soil can remove during
short application periods. The actual amount of phosphorus that can be retained in the
field will be at least two to five times the value obtained during a 5-day adsorption
experiment (Reed et al., 1995). Although the shaker experiments in this study were
conducted over a 2-day period, it was thought that improved performance would be
observed based on Reed et al.'s (1995) findings. Therefore, calcite and shale warranted
further study in column experiments.
Additional shaker experiments were required to better comprehend the adsorption process
of the substrates. The experiments were run at an initial concentration of 15 mg P0
4
L-
I
and sampled at 4, 8, 24 and 48 hours (Figures 4.4 and 4.5). Slag performed weIl at the
lower concentration of 15 mg P0
4
L-
I
, as it did at the higher concentrations of 0.5 and
5.0 g L-1. A discussion of the results for calcite and shale appears later.
4.4.3 Column experiments
4.4.3.1 Slag - lower influent concentrations
After 67 days of exposure of slag to a phosphate loading rate of 2 mg L-
I
, the substrate
continued to remove more than 90% of the influent phosphate (Appendix C). As of day
79, the influent phosphate concentration was increased to 5 mg L-
I
in an attempt to speed
up the saturation of the substrate. The mean phosphate concentration in the feeding
solution was 1.45 mg L-
I
during the first 78 days, and was 5.1 0 mg L-
I
as of day 79.
Around day 80, a filamentous material was noticed forming in the columns. The volume
ofthis material increased with time. The effluent became contaminated with this material.
As of day 112, it appeared as though saturation had been reached in the columns. On day
123 (February 12, 2001), higher phosphate concentrations were present in the effluent
than in the feeding solution. A filtered sample of the effluent was analysed. When
filtered, the phosphate concentration present was greatly reduced, suggesting that little
dissolved phosphate was present, and the majority of phosphate was present in a solid
51
60
50
"C
Cl)
>
~ 40
~
~ 30
.c
c.
en
o 20
.c
c.
~
0
10
0
4 8 24 48
Time (hr)
III Shale <4.75mm 0 Shale >4.75mm lm Calcite <6.35mm Calcite >6.35mm Slag >4.75mm
Figure 4.4 Shaker experiment results for slag, calcite and shale with an initial phosphate concentration of
15 mg L-
1
for 4,8,24 and 48 hours. 95% confidence intervals are indicated.
Calcite
18 9.60
16
9.40
(1)
14
9.20
-; "'012
9.00
-a ~ O
J:
en 0
8.80
o E 8
0.
~ 6
8.60
~
4
8.40
Cl
2
8.20
0 8.00
4 8 24 48
Time (hr)
..Calcite <6.35mm ~ Calcite >6.35mm -.- pH <6.35mm --$-- pH >6.35mm
Shale
48 24 8
-,-------------------------,- 8.20
8.10
8.00
7.90
7.80 J:
7.70 0.
7.60
7.50
7.40
'----+ 7.30
30
25
(1)
-; "d20
oC (1)
o.>
~ ~ 5
oC (1)
a.. ~ O
~
Cl
5
0
4
Time (hr)
_ Shale <4. 75mm ~ Shale >4.75mm -.- pH <4.75mm -.-. pH >4.75mm
Figure 4.5 Shaker experiment results for calcite and shale with an initial
1
sampied at 4, 8, 24 and 48 hours.
form, most likely the mysterious material forming in the columns (Table 4.9). Mann
(1997) attributed the high phosphorus adsorption capacity of slags to the formation of
stable calcium-phosphorus complexes at e1evated pH. It was suggested that perhaps the
solid forming was a calcium phosphate precipitate. A sample of the column effluent was
sent to Accutest Labs for analysis of phosphate in both a filtered and unfiltered sample. In
addition, the solid fraction was analyzed for calcium content to determine whether in fact
the solid was a calcium phosphate precipitate. The results of the phosphate analyses are
presented in Table 4.10. The analysis of the solid fraction showed that calcium was
present in the solid at a concentration of 90.64 mg L-
1
, and phosphate was present at
7.11 mg L-
1
, giving an approximate Ca/P ratio of 12.8. Calcium to phosphorus ratios of
sorne calcium phosphate compounds are presented in Table 4.11. The Ca/P ratio of the
solid fraction present in the effluent of the current study is much larger than the ratios of
the calcium phosphate compounds presented, making it difficult to identify the calcium
phosphate precipitate that had potentially formed.
Table 4.9 Phosphate concentrations in effluent samples from columns SL2-1, SL2-2
and SL2-3 taken February 2, 2001.
Unfiltered Filtered
P0
4
-P (mg L-
1
)
Standard Deviation
Port 1 8.685 3.398
2.929 2.101
Port 2 10.606 1.526
1.114 1.687
Port 3 10.689 1.246
0.543 1.103
Port 4 5.631 0.485
1.729 0.175
Table 4.10 Filtered and unfiltered samples from columns SL2-1 and SL2-2, analysed
for phosphate concentration (mg L-
1
) by Accutest Labs and the current study.
Date Sampie Accutest Labs Current Study
Feb.5,2001
Mar. 6, 2001
Mar. 15, 2001
SL2-2, Port 3
SL2-1, Port 3
SL2-2, Port 3
Unfiltered Filtered Filtered
37.17 3.14 2.95
21.03 1.74 0.94
19.00 1.16 0.84
54
Table 4.11 CalP ratios of calcium phosphate compounds (Roques et al., 1991).
Phosphate Formula Ca/P
Tricalcium orthophosphate Ca3(P04h 1.5
Octacalcium orthophosphate Ca4H(P04h 1.33
Dicalcium orthophosphate CaH(PO)4. 2H
2
0 1
Monocalcium orthophosphate Ca(H
2
P0
4
h 0.5
Hydroxyapatite Ca1O(P04MOHh 1.66
As of day 121 the effluents were filtered through 1.5 llm Whatman microfibre filters
before the phosphate content of the supernatant was determined. The columns showed
high phosphate sorption during the remaining experimental period, with a slight tendency
to decrease over time. The experiment was terminated on day 158 due to the time
limitations of the experiment. By the end of the experiment (158 days), the removal of
dissolved phosphate by the columns continued to exceed approximately 90%. Due to the
absence of any detectable phosphate breakthrough in the columns, geochemical modeling
of the effluent and calculation of saturation indices were not performed.
From the results of the experiment, it appears as though slag saturates from the top
downward (Appendix C). At the end of the experiment (day158), port 1 continued to
remove more than 35% of the dissolved phosphate, port 2 and port 3 approximately 70%
and port 4 approximately 90%. When the slag removed a high percentage of the
phosphate from solution, the variance of the mean percent phosphate removed in the three
columns was low. However, as saturation of the slag began, the three columns saturated
at different times, creating a larger variance of the mean percent phosphate removed.
As the slag's ability to remove phosphate decreased, so did the pH (Appendix C). The pH
decreased from an initial value of slightly more than Il, to just over 8. When Johansson
(1999) studied the phosphate sorption capacity of slag, similar observations of decreasing
pH with time were found. In Johansson's three columns, the pH decreased from an initial
value of slightly more than Il, to 9 in the first column, and to just over 8 in the other two.
Johansson (1999) explained a decreasing pH with saturation as the phosphate in the
solution that was added to the columns was present as H2P04-, and once the sorption sites
on the slag were filled, the phosphate and hydrogen ions passed through the columns,
thereby decreasing the pH in the outlet.
55
4.4.3.2 Slag - higher influent concentrations
A similar material formed in columns SL15-1, SL15-2, and SL15-3 as in SL2-1, SL2-2,
and SL2-3. In order to determine whether the material affected the dissolved phosphorus
readings, as of day 39 the effluent was filtered before the phosphate content of the
supernatant was determined. However, unlike the columns SL2-1, SL2-2, and SL2-3,
there was little difference of dissolved phosphorus present between the filtered and
unfiltered samples, except in port 4 (Table 4.12). Most likely, ports 1, 2, and 3 were
approaching saturation, but port 4 remained unsaturated. The suspended solids present in
solution before filtering affected the spectrometer reading, giving results such that it
appeared as though there was more phosphate present in solution than was actually the
case. When the effluent from port 4 was filtered, the dissolved phosphate present did not
equal the influent concentration, leading to the conclusion that port 4 had not reached
saturation.
Table 4.12 Phosphate concentrations in effluent samples from columns SL15-1,
SL15-2 and SL15-3 taken February 2, 2001.
Unfiltered Filtered
P0
4
-P (mg L-')
Standard Deviation
Port 1 16.506 15.240
0.437 0.264
Port 2 16.354 13.095
1.789 1.206
Port 3 13.095 12.472
1.121 1.330
Port 4 7.194 1.907
2.066 0.924
Similar to the observations made with columns SL2-1, SL2-2 and SL2-3, the trend that
slag saturates from the top downward was observed in the columns SL15-1, SL15-2 and
SL15-3 (Appendix D). At the end of the experiment (day 87), ports 1, 2, and 3 were
approaching saturation. However port 4 continued to remove more than 80% of the
dissolved phosphate. As was the case with columns SL2-1, SL2-2 and SL2-3, a similar
trend of decreasing pH with slag saturation was observed with columns SL15-1, SL15-2
and SL15-3 (Appendix D).
56
4.4.3.3 Calcite
The calcite columns began operating on December 1, 2000. The phosphate analysis for
the first two sampling dates (Day 6 and 13) showed that there was no phosphate removed
by the calcite substrate (Table 4.13). It was expected that calcite would remove phosphate
from the feed solution, as was the case with the shaker experiments, where 60 and 70% of
the initial phosphate was removed at 0.5 and 1.0 g L-
1
, respectively.
Table 4.13 Percent phosphate removal and pH measurements for columns CAlS-l,
CAIS-2 and CAIS-3. (Standard deviations are shown in parentheses).
Day 6 13
Date 01-Dec 13-Dec
% P0
4
Removal
Port 1 0 0
Port 2 0 0
Port 3 0 0
Port 4 0 0
PH
Port 1 7.90 (0.065) 7.85 (0.110)
Port 2 7.89 (0.068) 7.87 (0.146)
Port 3 7.90 (0.040) 7.88 (0.066)
Port 4 7.87 (0.053) 7.83 (0.036)
Based on the 1iterature, an attempt was made to determine which factors may be limiting
the calcite from sorbing phosphate. Reneau et al. (1989) reported that precipitation
depends on pH, concentrations of phosphorus, and reaction time. According to Stumm
and Morgan (1981), a pH range ofbetween 7.5 and 8.5 favours the chemical precipitation
of the various forms of calcium phosphates. Mann (1997) concluded in his study of
phosphorus adsorption characteristics of constructed wetland grave1s that a pH range of
7.0 to 8.0 would be suitable for the formation of calcium-phosphorus complexes. Since
the pH of the effluent of the calcite columns in the CUITent study (7.83 to 7.90) (Table
4.13) was in the range reported by Stumm and Morgan (1981) and Mann (1997) (7.0-8.5),
a comparison was made between the physical characteristics and experimental procedures
of authors who have been successful with the use of calcite as a phosphate sorber and
those ofthis study.
Brix et al. (2000) found calcite to have a high phosphorus-binding capacity. Drizo et al.
(1999) were successful with the use of limestone, a material composed largely of calcium
57
carbonate in the form of calcite, for the removal of phosphate from solution. Table 4.14 is
a comparison of the parameters of the current study versus those of other studies which
showed success with the use of calcite for the removal of phosphate from solution.
Table 4.14 Comparison of the physical properties and experimental conditions of the
current study with other studies.
. Current Study
PH 8.28
Bulk density (g cm-
3
) 1.66
Porosity (%) 48.7
Particle size (mm) 6.35-19.05
ICa (mg L-
1
) 15 (as K2HP04)
Retention time (h) 8
pH of effluent 7.83-7.90
Brix et al. (2000)
11.43
0.83
42.0
Nia
10 (as KH2P04)
12-14
7.5-8.5
Drizo et al. (1999)
7.80
Nia
33.0
60% > 12.70
35-45 (as K2HP04)
12
Nia
arc - influent phosphate concentration to columns.
The pH of the calcite used in the CUITent study was between that of the substrate used by
Brix et al. (2000) and Drizo et al. (1999). The bulk density of the calcite used in the
current study was higher than that used by Brix et al. (2000). However, these are fixed
parameters which could not be altered in the current study. The porosity of the calcite
used in this study was slightly higher than that used by Brix et al. (2000) and considerably
higher than that used by Drizo et al. (1999). The particle size range was similar to that of
Drizo et al (1999). The influent concentration was within the range used by the other
authors. The retention time was less in the current study. The pH of the effluent was
similar to Brix et al. (2000). From this comparison, it was decided to increase the
retention time in the columns to determine whether this was a significant condition in the
sorption of phosphate by calcite. As weIl, additional shaker experiments were performed
on calcite with a smaller particle size range, to determine whether the failure of calcite to
sorb phosphate was related to particle size.
In arder ta test the effect of retention time on the ability of calcite ta remove phosphate
from solution, the pumps feeding the columns were stopped. The effluents from each port
of each column were sampled as soon as the pumps were stopped, as weIl as at 4, 8, 24,
and 48 hours, and 6 days after pumping stopped. These times are represented by +0, +4,
+8, +24, +48 hours and +6 days. The pH of the samples was also taken. Appendix E
58
graphs the percent of phosphate removed with time for each port. The percent of
phosphate removed by the calcite ranged from 21 to 28% over the 6-day period. At the
first sampling (+0 h, port 4) 21% of the phosphate was removed. From the graphs in
Appendix E it can be seen that there appears to be a slight correlation with phosphate
removed and retention time. As the retention time increased from +0 to +24 hours, the
percent phosphate removed increased from 21.65 to 25.81 % (port 4). There also appears
to be a slight correlation with pH. As the pH increased, so did the phosphate removed.
Whether these differences prove to be statistically significant or not, the maximum
phosphate removed, 28%, is not a large enough phosphate removal to make it worthwhile
to use calcite as an adsorption substrate.
Shaker experiments were conducted to determine whether a smaller particle size would
contribute to an increased phosphate adsorption. Two particle sizes (0-6.35mm and
6.35-19.05mm) were shaken with a phosphate concentration of 15 mg L-
I
and sampled at
4, 8, 24 and 48 hours (Figure 4.5). The smaller calcite particle size performed better as a
phosphate adsorber. Drizo et al. (1999) had similar findings in their research on shale and
limestone. The trend may be explained by the material with the smallest particle size
distribution will have the highest surface area, increasing the potential for direct reaction
with phosphates (Drizo et al., 1999).
As was observed when varying the retention time in the columns, a correlation between
the pH and improved phosphate adsorption was observed in the shaker experiments. The
highest phosphate removal occurred in the smaller particle size at +24 hours and in the
larger particle size at +4 hours. The pH at both of these maximum adsorption points was
approximately 9.0. Again, whether these correlations prove to be statistically significant
or not is irrelevant since the maximum phosphate adsorption was approximately 16%,
which is too little to use as a phosphate adsorber. The calcite column study was
terminated, and it was concluded that calcite, as per the results ofthis study, would not be
an effective phosphorus adsorption substrate.
59
4.4.3.4 Shale
The shale columns began operating December 1, 2000. As was the case with the calcite
columns, the phosphate analysis for the first two sampling dates (Day 6 and 13) showed
no phosphate removal by the shale substrate (Table 4.15). Given that the results of the
shaker experiments showed a phosphate removal of approximately 50% and 69% with
initial phosphate concentrations of 0.5 and 1.0 mg L-
1
, respectively, it was expected that
shale would remove phosphate from solution in the column experiments. Drizo et al.
(1999), in their study of seven substrates examined for their phosphate removal capacity,
found shale to have the highest phosphorus adsorption capacity and concluded that shale
had the best combination of properties for use in constructed wetland systems and the
greatest potential for phosphorus removal. A comparison between the physical
characteristics and experimental procedures of the CUITent study and that of Drizo et al.
(1999) was made (Table 4.16) in an attempt to determine why shale was not successful at
removing phosphate from solution in this study.
Table 4.15 Percent phosphate removal and pH measurements for columns SHI5-1,
SH15-2 and SHI5-3. (Standard deviations are shown in parentheses).
Day 6 13
Date 01-Dec 13-Dec
% P0
4
Removal
Port 1 0 0
Port 2 0 0
Port 3 0 0
Port 4 0 0
pH
Port 1 7.76 (0.078) 7.37 (0.096)
Port 2 7.75 (0.020) 7.76 (0.075)
Port 3 7.70(0.115) 7.70 (0.086)
Port 4 7.69 (0.153) 7.71 (0.026)
Table 4.16 Comparison of the physical properties and experimental conditions of the
current study with that of Drizo et al. (1999).
Current Study
PH 8.56
Bulk density (g cm-
3
) 1.66
Porosity (%) 56.6
Particle size (mm) 4.75-38.10
ICa (mg L-
1
) 15 (as K
2
HP0
4
)
Retention time (h) 8
pH of effluent 7.37-7.76
arc - influent phosphate concentration to columns.
60
Drizo et al. (1999)
4.50
Nia
37.7
65% > 6.80
35-45 (as K
2
HP0
4
)
12
Nia
The pH and porosity of the shale used in the current study were higher than that used by
Drizo et al. (1999). The particle size range was similar to that of Drizo et al. (1999). The
influent phosphate concentration and the retention time were less in the current study.
From this comparison, it was decided to increase the retention time in the columns to
determine whether this was a significant condition in the sorption of phosphate by shale.
As well, additional shaker experiments were performed on shale with a smaller particle
size range to determine whether the failure of shale to sorb phosphate was related to
particle size.
The same methodology was used to test the effect of an increased retention time as that
used for calcite. The pumps feeding the columns were stopped and the effluents from
each port of each column were sampled as soon as the pumps were stopped, as well as at
4, 8, 24 and 48 hours, and 6 days after pumping stopped. These times are represented by
+0, +4, +8, +24, +48 hours and +6 days. The pH of the samples was also taken. Graphs of
the percent of phosphate removed with time are presented in Appendix F. The percent of
phosphate removed by the shale ranged from 22 to 34% over the 6-day period. At the first
sampling (+0 h, port 4) 22% of the phosphate was removed. From the graphs in Appendix
F it can be seen that there appears to be a correlation with phosphate removed and
retention time. As the retention time increased from +0 hours to 6 days, the percent
phosphate removed at port 4 increased from 22.33 to 31.13%. There does not appear to be
any correlation with pH. For instance, at port 2 at +4 hours and +8 hours, the pH was
measured as 7.76 and 7.83, respectively, however, the percent phosphate removed
remained approximately the same, 26.08 and 26.05%. Whether these differences prove to
be statistically significant or not, the maximum phosphate removed, 34%, is not a large
enough phosphate removal to make it worthwhile to use shale as an adsorption substrate.
Shaker experiments were conducted to determine whether a smaller particle size would
contribute to an increased phosphate adsorption. Two particle sizes (0-4.75 mm and
4.75-38.10 mm) were shaken with a phosphate concentration of 15 mg L-
1
and sampled at
4, 8, 24 and 48 hours. The smaller particle size performed better as a phosphate adsorber
(Figure 4.5). This agrees with Drizo et al.' s (1999) findings, as explained previously in
61
the discussion on calcite. However, although the smaller particle size outperformed the
larger size, the maximum phosphate removal observed was only approximately 25%. Due
to the overall poor performance of shale, the column study using shale was terminated
and it was concluded that shale, as per the results of this study, would not be an effective
phosphorus adsorption substrate.
62
5. CONCLUSIONS
5.1 Summary
The Alfred Municipal Wetland was monitored to determine its treatment capacity for
BOD
s
, N0
3
-N and N0
2
-N, NH
3
and NH
4
, TKN, TSS, TP, O-P0
4
, fecal coliforms and E.
coi!. Soil, plant and water samples were collected from the wetland cells to determine the
nutrient partitioning of phosphorus and nitrogen within each cell. Phosphate adsorption
measurements and column experiments were conducted to determine the phosphate
removal efficiency of various media. This would aid in the selection of a substrate to
incorporate in a phosphorus adsorption filter to be used as a phosphorus polishing step in
the constructed wetland system. As a result of the study, the following conclusions were
formed:
5.2 General Conclusions
The average removals for the parameters monitored in the wetland cells from May
to November 2000 are as follows: BOD
s
34%, TKN 37%, NH
4
-N 52%, TSS 93%,
TP 90%, O-P0
4
82%, fecal coliforms 52% and E. coli 58%. TN, TP and BOD
s
were reduced to levels below the maximum permissible levels required for direct
discharge to the Azitica Brook (TN < 3 mg L-
1
, TP < 0.3 mg L-
1
, BODs
< 3 mg L-
1
).
Plant uptake and sediment sorption appeared to have both contributed to the
removal of phosphorus and nitrogen from the wastewater.
The vegetated filter strip was not effective at reducing phosphorus concentrations
in the wastewater. It did succeed, however, at reducing BOD
s
, TKN, NH
4
-N, TSS,
FC and E. coli to 10wer effluent 1eve1s by 18%, Il %, 28%, 22%, 28% and 22%,
respectively. It therefore serves as a polishing step to the wetland cells for these
mentioned pollutants.
63
The three slag filters installed as part of the constructed wetland system were
effective phosphorus adsorbers, removing up to 99% of TP in the wastewater.
The monthly groundwater samples indicated that the samples taken from the
location nearest the lagoons showed higher TKN, NH
3
-N and N0
3
-N
concentrations.
Slag was found to be the best choice of the three substrates studied for phosphorus
adsorption based on the shaker experiments. It showed the greatest phosphate
adsorption capacity (24.22 mg g-l) of the substrates tested.
In the column studies, slag continued to remove more than 90% of the influent
dissolved phosphate. Slag was found to be the best choice of the three substrates
studied for phosphorus adsorption based on the column studies.
Calcite removed up to 70% of the initial phosphate in the shaker experiments.
However, it removed less than 28% of the influent dissolved phosphate in the
column studies.
Shale removed as much as 69% of the initial phosphate in the shaker experiments.
It removed less than 25% of the influent dissolved phosphate in the column
studies.
64
6. DIRECTIONS FOR FURTHER RESEARCH
As a result of the study, the following recommendations for further research are made:
1. To determine the long-terrn treatment capacity of the Alfred Municipal Wetland,
regular monitoring of BOD, N0
3
and N0
2
, NH
3
and NH
4
, TKN, TP, O-P0
4
, fecal
coliforms and E. coli should continue. This will also aid in the determination of the
length of time it takes the wetland to become saturated with phosphorus. Based on the
findings, a decision may be made as to whether a large-scale constructed wetland
system would be an effective solution as a wastewater treatment step for the Village
of Alfred.
11. To determine and understand the removal mechanisms of pollutants in the Alfred
Municipal Wetland, a sampling of sediment, plant and water should take place on an
annual basis.
iii. Continue the monitoring of the pilot-scale slag filters to determine the maximum
adsorption capacity of the slag substrate. This would prove useful in the design of
full-scale slag adsorption filters.
IV. The pH of the effluent of the slag columns reached a maximum of Il.52. The pH of
the pilot-scale slag filters should be measured and corrected if required before
discharging to surface waters.
v. To determine the phosphorus removal capacity of the vegetated filter strip, tests
should be made with effluents ofhigher phosphorus concentrations.
VI. T0 determine whether leaching of the pollutants from the wetland system is occurring,
regular monitoring of the groundwater surrounding the wetland system should
continue.
65
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Richardson, C.J. 1985. Mechanisms Controlling Phosphorus Retention Capacity In
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nd
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71
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72
AppendixA
Figures of nitrogen and phosphorus concentrations of the
sediment, plant and water samples taken from the wetland cells
73
1 13 m 1 14 m 1 13 m 1
..
, i i ,
No sediment
samples taken
in the Aerobic
Basin
1
1
1
1
1 1

1 1
1 1
1 1
1 1
1 1
1 1
1 1
1
1
1
1
1
1
1
1
1
1 1

1 1
1 1
-E-- Free-surface
Wetland 1
78 m
-E-- Free-surface
Wetland Il
0.00
1 13 m 1 14 m 1 13 m 1
..
, : ! ,
20 m
20 m
t
20 m
t
20 m
+
18 m
t
N=1535: 1192 : 2708
1
20 m 03-N=09
3
0.09 : 0.01
t
H4=23.64 10.30 : 15.84
--------+----------l---------
1375 : 1403 : 1636
1 1
1 1
: 0.09 : 0.63
1 1
7.12 : 7.26 : 8.10

1 1
1688 : 1624 : 1736
1 1
0.59 : 1.30 : 0.30
1 1
1 1
9.99 : 8.66 : 13.17

1 1
1 1
0.19 : 0.10 : 0.01
1 1
1956 : 2
1
35 !
18
36
1531
0.08
20.03
0.20
trN=831: 1154
1
N03-N=0 1:7 0 10
1
1
NH4=15.51 18.23
1 1
--------j------------------
1 1
1166 : 1561: 681
1 1
1 1
: 0.06: 0.13
1 1
24.76 : 28.05: 18.32
1
78 m
40 m
l
1"
13m 13m 13m
Figure A.1 Sediment nitrogen concentrations in each subplot of the Alfred Municipal Wetland. Values
appear in order from top to bottom in each subplot as total nitrogen, nitrates, and amonium. Ali values are
in mg/kg.
<-- Free-surface
Wetland 1
78m
857
14.03
<-- Free-surface
Wetland Il
817
12.46
1 13 m 1 14 m 1 13 m 1
...
, i i ,
20 m

20 m
+
18 m
t
20 m
+
! 738
20
ehlich- i 6.37
m =8.53 :
+
--------t----------l---------
739 : 755 : 796
1 1
1 1
5.68 : 9.75 : 13.30
1 1
1 1
1 1

1 r
: 796 : 813
1 1
: 10.24 : 13.26
1 1
1 1
1 1
1 1
--------+----------,---------
914 i 801 ! 830
r 1
18.19 : 7.47 : 8.82
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1

1 r
1 1

samples taken
----- in the Aerobic ----
Basin 1
i
1 1
1 1
r 1
1 1
1 1
--------+----------,---------
1 1
1 1
1 1
1 1
1 1
1 1
1 1
TP=703
1 1
1
711
1
756 1 1
Mehlich-
1 1
1 1
1
2.19
1
4.21
P=1.58
1 1
1 1
1 1
1 1

1 1
705
1
740
1
710
1 1
1 1
2.38
1
2.95
1
1.85
1 1
1 1
1 1
1 1
1 1
1 13 m 1 14 m 1 13 m 1
...
78 m
40 m
l
1'"
13 m 13 m 13 m
Figure A.2 Sediment phosphorus concentrations in each subplot of the Alfred Municipal Wetland. Values
appear in order from top to bottom in each subplot as total phosphorus and Mehlich phosphorus. Ali
values are in mg/kg.
1 13 m 1 14 m 1 13 m 1
...
i i ,
No plant
samples taken
in the Aerobic
Basin
1
1
1
1
1 1
--------T----------4---------
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1
1
1
1
1
1
1
1
1
1 1

1 1
1 1
Free-surface
Wetland 1
78 m
Free-surface
Wetland Il
1136
5717
20 m
20 m
+
18 m
t
20 m
+
1 13 m 1 14 m 1 13 m 1
...
T
P=1036: 1097 : 1093
1 1
1 1
20 m N=11104i 8755 ! 22103
+
--------f----------l---------
1372 : 1343 : 1093
1 1
15643 i 12415 i 6392
1 1
1 1
1 1
--------T----------4---------
1 1
: 1347 : 1023
1 1
: 11649 : 6526
1 1
1 1
1 1
1 1
--------T----------4---------
1557 i 1328 i 1714
1 1
7317 : 7787 : 8802
1 1
20 m
+
967
10004
1008
10702
1
: 853
5339
1
1
1 1
--------T---------4---------
1 1
: 1257 : 852
1 1
i 11037 i 9373
1 1
1 1
1 1
40m
78 m
l
1'"
13m 13m 13m
Figure A.3 Plant phosphorus and nitrogen concentrations in each subplot of the Alfred Municipal Wetland.
Values appear in order from top to bottom in each subplot as total phosphorus and total nitrogen. Ali
values are in mg/kg.
1 13 m 1
14 m 1 13 m 1
1 13 m 1
14 m
1 13 m 1
.. .. .. ..
N03-N=0.do 0.00
1
0.00
T
03-N=0.do 0.00
1
0.00 1 1
1 1 1 1
1 1 1 1
NH4=0.08 : 0.07
1
0.07
20 m
H4=0.11 : 0.09
1
0.14
1 1
1 1 1 1
n- KN=0.57 : 0.57
1
0.60
t
KN=1.85 : 1.14
1
1.6 1 1
1 1 1 1

0.00
1
0.00
1
0.00
1 1
1 1
0.00
1
0.01
1
0.00 1 1 1 1
0.07
1
0.07
1
0.07
1 1
1 1 1 1
1 1
20 m
0.12
1
0.22
1
0.32
1 1 1 1
78 m 1 0.80
1
0.62
1
0.44
t
1 1 1 <E-- Free-surface 1 1
_J..J___ _____i--L2_t?___ 78 m 1 1
- - - - - - - - - --- - ---1---- -----
Wetland 1
0.00 i 0.00 : 0.00
1 1 1
0.00 : 0.00 : 0.00
0.07
1 1 1 1
1
0.16
1
0.08 0.10
1
0.10
1
0.38 1 1
20 m
1 1
1 1 1 1
0.55
1 1
+
1 1
1
0.71
1
0.69 1.85
1
2.30
1
2.83
1 1 1 1
--..
1 1 1 1
1 1 1 1
0.07
1
0.07
1
0.07
18 m
0.18
1
0.09
1
0.15
1 1 1 1
1 1
t
1 1
1 1
') JI 1 ! ') QI:: ! ') ')':1
N03-N=0.OO
1
1
NH4=0.07 :
20 m
1
KN=0.73 : 0.66 1.03
t
<E-- Free-surface
1 1
40 m

1 1
0.00
1
0.00
1
0.00
Wetland Il
1 1
1
1 1
0.08
1
0.07
1
0.08
1 1
20 m 1 1
1 1
..-1..
0.78
1
0.71
1
0.92 1 1
1"

13 m 13 m 13 m
Figure A.4 Water nitrogen concentrations in each subplot of the Alfred Municipal Wetland. Values appear
in order from top to bottom in each subplot as nitrates, ammonium, and total Kjeldahl nitrogen. Ali values
are in mg/L.
<E---- Free-surface
Wetland 1
78 m
0.07
<E---- Free-surface
Wetland Il
1
1
1
1
: 0.25
1
1
1
1 1
--------T----------,---------
1 r
r 1
1 1
1 1
0.10 : 0.11 : 0.15
1 1
1 1
1 1
1 r
- - - -- - -- T ---- ----- - -1-- - - - - ---
1 1
1 1
1 1
0.12 : 0.41 : 0.15
1 r
1 1
1 1
1 1
1 1

1 1
1 1
0.19 : 0.18 : 0.18
1 1
1 1
1 1
1 13 m 1 14 m 1 13 m 1
... .... .... .
, i , ,

20 m
T
lm
20 m
+
18 m
t
20 m
+
1
1
1
trP=0.04 i 0.04 i 0.03
1
1
1
1 1
--------T----------,---------
1 1
1 1
1 1
0.02 i 0.02 i 0.03
1 1
1 1
1 1
1 1

1 1
1 1
1 1
0.03 : 0.01 : 0.01
1 1
1 1
1 1
1 1
1 1

1 1
1 1
0.04 : 0.02 : 0.03
1 1
1 1
1 1
1
1
tr
P=0.02 : 0.05 : 0.05
1
1
1
1
1
1 1
--------T---------,---------
1 1
1 1
1 1
0.01 : 0.02 : 0.07
1 1
1 1
1 1
1 1
1 1
1 13 m 1 14 m 1 13 m 1
... .... .... .
, i i ,
78 m
40 m
l
1'" .,... 1'" 1
13m 13m 13m
Figure A.S Water total phosphorus concentrations in each subplot of the Alfred Municipal Wetland. Ali
values are in mg/L.
Appendix B
Influent and effluent concentrations from
different stages in the Alfred Municipal Wetland
79
15
-
13
...J
11
-
C)
E 9
-Il)
7
C
0
5
al
3
1
19-Apr 8-Jun
(a) B005
28-Jul 16-Sep
Date
5-Nov 25-Dec
--+-Lagoon --IlI-FSW liN AB IN
mmf(_mFSW Il IN .....-FSW Il EFF -.-VFS EFF
(b) TKN
3
2.5
-...J
2
-
C)
E
1.5
-
Z
~
1-
0.5
0
19-Apr 8-Jun
--+-Lagoon
FSW Il IN
28-Jul 16-Sep
Date
--Ill- FSW 1IN
.....-FSW Il EFF
5-Nov
AB IN
-.-VFS EFF
25-Dec
Figure B.1 Influent and effluent concentrations of BOOs and TKN from
different stages in the Alfred Municipal Wetland at each sampling date from
May 19 to November 3,2000.
(a) NH4
5-Nov 25-Dec 8-Jun 28-Jul 16-Sep
Date
o. 07
0.02
19-Apr
0.27 ,..--,.-----------------,
0.22 +---+-----!'==""I-----------------I
-...J
-
0.17
-
J!: 0.12
Z

FSWIIIN
-B-FSW liN
--.- FSW Il EFF
ABIN
--e-VFS EFF
(b) TSS
302 -r---------------------,
252
-
=, 202 +---------\--+-\-----------____1
.. 152
102 +--------"'C-/--\-----------____1
1-
52
2
19-Apr 8-Jun 28-Jul 16-Sep 5-Nov 25-Dec
Date

FSW Il IN
-B-FSW liN
--.- FSW Il EFF
ABIN
--e-VFS EFF
Figure 8.2 Influent and effluent concentrations of NH
4
and TSS from
May 19 to November 3, 2000.
(a) TP
2.01
-
1.51
..J
-
C)
E 1.01
-
c.
t-
0.51
0.01
37000 37050 37100 37150 37200 37250
Date
-+-Lagoon -B-FSWIIN ABIN
FSWIIIN ~ F S W I I EFF --e-VFS EFF
-t-Slaa 1 -Slaa2 -Slaa3
(b) O-P04
"-
~
\
-
\
/ \
~
_..... .1_
-
l.
3.51
_ 3.01
..J
C, 2.51
.. 2.01
a 1.51
q. 1.01
o 0.51
0.01
19-Apr 8-Jun
-+-Lagoon
FSW!lIN
-+-Slag 1
28-Jul 16-Sep
Date
5-Nov 25-Dec
Figure B.3 Influent and effluent concentrations of TP and O-P0
4
from
May 19 to November 3, 2000. Breaks in the graph indicate that the pollutant
was not measured during these periods.
(a) Fecal Coliform
28-Jul 16-Sep 5-Nov 25-Dec
Date
260 ..,.--------------------,
:g 21 0 ----_f_t__-----__I
:=0
'0 160
0-
U 11 0
CJ ::::s
8 60
u. _
10 +--..,iL
19-Apr 8-Jun
-+-Lagoon -B-FSW liN AB IN
FSW Il IN --.- FSW Il EFF -.-VFS EFF
(b) E.coli
25-Dec 5-Nov 28-Jul 16-Sep
Date
8-Jun
10 +----L; LL
19-Apr
::J' 210 ..,---------------------,
E
g 160
't""
]i
C 11 0 ----I_+------___1
::::s
o
CJ
-
:.:::::
o
CJ
LLi
-B-FSW liN
--.-FSW Il EFF
ABIN
-.-VFS EFF
Figure 8.4 Influent and effluent levels of Fe and E. cali fram different
stages in the Alfred Municipal Wetland at each sampling date fram May 19
ta Navember 3,2000.
Appendix C
Column experiments - slag - lower influent concentrations
84
100
.. .......
'0
CD
80
>

0
E
CD
60

0::

S

ca
.r::
40
Q.
th
0
.r::
20 C-
'fl
0
.a __
-
...
-- -
1
0 50 100 150 200
Time (days)
8
10
12
11
J: 9 +-------------+-----+".......
Q.
7 -J--------------------------,
200 150 100
Time (days)
50
6+-------,.------.,--------,,...------
o
Figure C.1 Mean percent phosphate removed and pH at port 1 for columns
SL2-1, SL2-2, and SL2-3. The arrow indicates the place when the effluent
samples were filtered before being analysed. Breaks in the graph lines
indicate that pH was not measured during these periods.
100
..... ."",. ....
'0
CI)

>
80
0
E

..

CI)
0::
60

.s

eu
.c:
c.
40
tn
0
.c:
Q.
20
~
0
0

--- -
0 50 100 150 200
Time (days)
12
11
10
J:
9
c.
8
7
6
0 50 100 150 200
Time (days)
100 .........
1*' ....

"'C
(J)
80
>
0

E

(J)
0:: 60
(J)
-
eu
.c
40
c.
tA
0
.c
C.
20

CI
o-
.--.
0 50 100 150 200
lime (days)
200 150 100
lime (days)
50
12 ...-..- ..---.
11
10
i 9 +------
8 +--- __"'"-""L I
7 -1-------------------------1
6+-------r---------,------,-------i
o
+
100
.,....... ~ .
. .. .

'0
Cl)
80
>

0
E

Cl)
0:: 60
S
eu
oC
40
c.
fi)
0
oC
0.
20
~
0
0
0 50 100 150 200
lime (days)
12
, . . , . , . , . , . , . , . ~ - , . , . , , , ~ " " ' ..,,.,.-,
11
10
- - - ~ -
:I:
9
~ _ . _ - ~
c.
8
7
6
0 50 100 150 200
lime (days)
Appendix D
Column experiments - slag - higher influent concentrations
89
100
"C
CD
80
>
0
E
CD
60
IX:
w
--------,
w
S
eu w
J:
40
Q.
t/)
W W
0
W
W
J:
20
C-

~
Ww
Cl
w
w
w
w w
0
,..w
er-----w 1
~ - - - ~ - - - - I
0 20 40 60 80 100
Time (days)
12
11
10
::I:
9
Q.
8
7
_.__.,.
6
0 20 40 60 80 100
Time (days)
Figure 0.1 Mean percent phosphate removed and pH at port 1 for columns
-------------.-------
100
"'C
Q)
80
>
0
E
Q)
60
0::
-
Q)
-
C'Cl
J:
40
c.
t/)
0
J:
20
a.
0
0
0

20
40

60
80 100
Time (days)
11
8 ---------'=---
10 +------/-----\----------------
i 9
7
100 80 60 40 20
6+----...,..-----,------,-----.,-------1
o
Time (days)
100
80
60
40
20
_ ~ ~ _ ~ _ ~ . _ ~ __..JIIU.IJ---- _. __. _
- 1 - ~ ~ . ~ - " " " - .
- 1 - ~ ~ ~ ~ . ~ ~ ~ ~ ~ - - ~ ~ ~ ~ ~ - - - - - - - -
100
"C
CI)
80
>
0
E
CI)
60
0:::
.s
CI:S
J:
40
Q.
m
0
J:
20
a.
~
1 0
1
o~
0
Time (days)
12
11
10
J:
9
Q.
8
7
6
0 20 40 60 80 100
Time (days)
100

~

"C

CI>
80

>
0

E
CI>
60
0:::
S
eu
oC
40
c.
tn
0
oC
20
a.
~
0
o-
0 20 40 60 80 100
Time (days)
12 -,-------------"-'--------,
11 +-------------------1
10 I ............- - - - . . . . ~ _ : : _ ~ ~ ~ -
J: 9 -1---------+----+_.__-J-----------1
C.
8 + - - - - - - - - - - - - - - - - - - - - - ~
7 +---
100 80 60 40 20
6+----..,..----.,...----,-----,------1
o
Time (days)
Appendix E
Column experiments - calcite
94
29 --,---------- ------------------------------------------ --- ----------- --
"C
~ 28 - -------------------------------.---
~ 27 +-----------------------. ----------
~ 26
~ 2 5 - + - - - - - - - - - . - - - - - - - - - - - - - - - - -
-a 24 + - - - - - - - - - - - - - - - - - - - - - - ~ - - - - -
t/)
~ 23 + - - - - - - - - - - - - - - - - - - - - - . - - - - - ~ - -
Q.22-+--------------------------
~
21
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
7.85
------_.- ------------
7.80
7.75 -
::I:
7.70
c.
7.65
7.60
7.55 1
~ - - ,
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
Figure E.1 Mean percent phosphate removed and pH for columns CA15-1,
CA15-2 and CA15-3 combined for port 1.
1------------------------------------------- --
29 - , - - - - - ~ - - - - - - - - - - - - - - - - - - -
"C
~ 28 -t----------------------------
~ 27 +---------------------------------
~ 26 - t - - - - - - - - - - - - - - - - - - - - - ~ - - - - - . - - - - -
.; 25 +------.1---------- --.- -------------

-a 24 --i----- --------------
en
~ 23 -+---------------------------------------------------
c.. 22
?J,
21 + - - - - , - - - - - - - - , - - - - - ~ - - - ~ - - - _ _ _ , _ - - - - -
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time
+6 d +48 hr +24 hr
~ ~ - - - - - - - - - - - - - - - - - - - - - - -
+8 hr
+----------------------- -- ---
-,-----------------------------
+---------------------------
+ - - - - - , - - - - - - ~ - - ~ - - - ~ - - - ~ - - - - - - - - - - - - - - ,
7.90
7.85
7.80
7.75
-----
::I:
7.70
c.
7.65
7.60 -
7.55
7.50
+0 hr +4 hr
Time
29
'0
(1)
28
>
0
27
.------

E
---
(1)
26
0:::
(1)
25
-
-
eu
-a 24
t/)
0
23
.c
a.
22
0
21
-----,
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time
7.90 --,--------------
7.85 +------------------------/"'-----
7.80 +--
7.75 +------F-----------'lL--------------
7.70 +------+---------------------
7.65 +---J-------------------------"---------
7.60
7.55 +------------------------
7.50
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time
-g 29
28 +----------------------
E 27 +--------------------
CI)
: 26 +- e"'"------
25 +--------------.-
-a 24 +------
23 t--------------e----- ------------------
if 22 +-----.- -----------------------
21 -1
o
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
7.90 ,----------------------------.--
7.85 +--------------------
7.80 +--------"'.........
i 7.75 +-------/'
7.70 +--------------------------------------------- ------
7.65 +--------
------------------------ ---------_..
7.60
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
Appendix F
Column experiments - shale
99
37 --.--------------------.----.----------------
"C 35 +-------------------.---.---.---------
~ .
~ 33 +---------------------- --------
E
~ 31 +----------------------------
S29+-------------
eu
.r::
~ 27 -I-------------------t-------
o
if 25 -t--.;----------------------
'*' 23 ...j-------------------.----------
21 -1----,----------,-----,--------.----------,------1
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time
+6 d +48 hr +24 hr +8 hr
..,------,--------,----------1- -
._-------- ---_._------------ ------
+4 hr
--+-----------------------------
--.--------------------------- ------------_..
7.90
7.85
7.80
7.75
:::c
Q.
7.70
7.65
7.60
7.55 t
+0 hr
Time
Figure F.1 Mean percent phosphate removed and pH for columns SH15-1,
SH15-2 and SH15-3 combined for port 1.
33
-------_.

"C
(1) 31 +----------------------
>
o
29 +-----------------.-------
.
S 27 +---------------.----------
.
.s:::
C-
m 25 +------''''IJ-----------------
o
.s:::
C. 23
21
+0 hr +4 hr +8 hr +24 hr +48 hr
Time
+6 d
7.95
7.90
7.85
7.80
:::c
7.75
C-
7.70
7.65
7.60
7.55
.._---
--_._-_.-
_._.. __..._------_._-_.-

+---------------------_._._---

+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time
35
"'C 33 ------------ -------
e
>
31
a:: 29 +-------------------------
.e
cu
oC 27
Q. e e
U)
25 +--_=e -=e -------
a.
?fl. 23 +---------------------- --------
21 --1
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
,------- -----------,
---------------------------
--------
8.00 -,----------------
7.95 +---------------- -------/=
7.90
7.85
J: 7.80
Q. 7.75
7.70 +--,.",L-----
7.65
7.60 +--------------------------- ---
7.55
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
lime
Figure F.3 Mean percent phosphate removed and pH for columns 5H15-1,
5H15-2 and 5H15-3 combined for port 3.
+6 d +48 hr
e
- ~ - - - - - - - -
e
+24 hr
e
+8 hr
I - - - - - - - - - - . . . - - - - - ~ - - - ~ - - - - - - ---- -
1--------,----,-----,----,-------,------,
+- e _
33
"C
31
Cl>
>
0
E
29
Cl>
0::
.s
27
--------
C'll
.s:::
C-
UI
25 -
0
.s:::
::1
Q.
~
0
e
+0 hr +4 hr
lime
8.00 -1
7.95 + - - ~ - -
:.:: J....----------------
---------------
7.80 + - - ~ I ' - - - - - - - - - - - - - - - - - - - - - - - - - - -
7.75 + - - - - - - - - - - - - - - - - - - - - - - ~ -
7.70 -1---------------
7.65 +-----.-----,--------,--------,------,----------------1
+0 hr +4 hr +8 hr +24 hr +48 hr +6 d
Time

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THE EFFICIENCY AND MECHANISMS FOR POLLUTANT REMOVAL IN

BIOLOGICAL WASTEWATER TREATMENT SYSTEMS

% Phosphate removed fram solution

.; 25 +------.1---------- --.- -------------

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